JP2012025938A - Porphyrazine pigment, ink composition, recording method, and colored body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink having an excellent hue as a cyan ink, which is excellent in light resistance, ozone resistance and humidity resistance, and suitable for ink jet recording.SOLUTION: This invention relates to a porphyrazine pigment represented by formula (1), having the maximum absorption wavelength in the range of ≥598 to ≤606 nm when measuring an absorption wavelength using a spectrophotometer having the wavelength range of 400-800 nm, or relates to a mixture of salts thereof. [In the formula, rings A-D are each independently a benzene ring or a pyridine ring].

Description

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

In recent years, materials for forming color images have been mainly used as image recording materials. Specifically, recording materials for color images are prominent in recording materials used in ink jet systems, electrophotographic systems, etc .; thermal transfer type image recording materials; transfer type silver halide photosensitive materials; printing inks; Has been used. In addition, color filters are used in LCDs (liquid crystal displays) and PDPs (plasma display panels) in displays, and in electronic parts such as CCDs (imaging elements) in photographing equipment. In these image recording materials and color filters, in order to reproduce or record a full-color image, dyes and pigments are appropriately used as the three primary colorants of the additive color mixture method and the subtractive color mixture method. However, the fact is that there is no dye having excellent light fastness that can withstand various use conditions, and has a light wavelength absorption characteristic that can realize a preferable color reproduction range, and improvement is strongly desired.

  Among various color recording methods, various ink ejection methods have been developed for a recording method using an ink jet printer, which is one of the representative methods, that is, an ink jet recording method. In any of these methods, ink droplets are generated and recorded on various recording materials such as paper, film, and cloth. In this method, since the recording head and the recording material are not in direct contact with each other, no noise is generated and the method is quiet. In addition, due to the features of miniaturization, high speed, and easy colorization, it has been spreading rapidly in recent years, and significant growth is expected in the future. Conventionally, as inks such as fountain pens and felt pens and inks for ink jet recording, inks in which a water-soluble dye is dissolved in an aqueous medium as a pigment are used. In these water-based inks, a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle. These inks provide a recording image with sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, have little bleeding, and have excellent storage stability. Is required. In addition, there is a demand for various fastnesses such as water resistance, moisture resistance, light resistance, and gas resistance that the bronze phenomenon does not occur in the formed recorded image. In addition, high solubility in water, solvents and additives is one of the properties required for pigments.

  The bronze phenomenon refers to a phenomenon in which the dye becomes flakes on the surface of the recording material due to the association of the dyes or poor ink absorption. When this phenomenon occurs, the gloss, print quality, and print density are all inferior. In particular, when a metal phthalocyanine dye is used as the dye, it often appears as a “red floating phenomenon”, and the color balance of the entire image becomes non-uniform and the quality thereof is lowered. In recent years, glossy paper is often used as a recording medium having a texture close to that of a silver salt photograph. However, when a bronze phenomenon occurs, the glossiness on the surface of the recorded material varies, and the texture of the image is significantly impaired. . From such a viewpoint, a pigment that does not cause bronzing is strongly desired.

Applications of inkjet printers have been expanded from small OA printers to large industrial printers, and more robustness such as water resistance, moisture resistance, light resistance and gas resistance is required more than ever. ing. The water resistance has been improved by a method of coating the surface of a recording material with inorganic fine particles capable of adsorbing a dye in an ink such as porous silica, cationic polymer, alumina sol or special ceramic together with a PVA resin. However, since there are many opportunities to use a recording material such as plain paper whose surface is not coated, development of a dye having excellent water resistance is desired. Moisture resistance refers to resistance to a phenomenon in which a dye in a recording material oozes when the colored recording material is stored in a high humidity atmosphere. When there is a blur of the dye, the image quality is remarkably deteriorated particularly in an image that requires a high-definition image quality such as a photographic tone. Therefore, it is important to reduce such a blur as much as possible. A technology for greatly improving light resistance has not yet been established, and the improvement is one of the problems. In addition, with the recent penetration of digital cameras, there are increasing opportunities for inkjet recording with photographic image quality even at home, and when images are stored, the discoloration of images due to oxidizing gas in the air is also a problem. Has been. This oxidizing gas reacts with the dye on the recording paper or in the recording paper, and discolors the recorded image. Among oxidizing gases, ozone gas is regarded as a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Since this color fading phenomenon is characteristic of ink jet images, improvement of ozone resistance (gas) is also an important issue.

Typical water-soluble cyan dyes used in cyan ink for ink jet recording are phthalocyanine and triphenylmethane. Among these, phthalocyanine derivatives classified as A to H below are known as typical phthalocyanine dyes.

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

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

D: phthalocyanine-based coloring matter described in Patent Literature 5 and the like, [for _{example, Cu-Pc- (SO 3 H} ) m (SO2NR 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) 1 (SO ₂ NH ₂ ) m (SO ₂ NR ¹ R ² ) n; l + m + n = 0 to 4 ].

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

G: Phthalocyanine dyes described in Patent Documents 8, 9, and 12, etc. [phthalocyanine compounds in which the substitution position of the substituent is controlled, phthalocyanine dyes in which a substituent is 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.

C. currently used for inkjet recording is widely used. I. Direct Blue 86 or C.I. I. Phthalocyanine dyes represented by Direct Blue 199 are generally characterized by being excellent in light resistance compared to magenta dyes and yellow dyes. However, phthalocyanine dyes have a greenish hue under acidic conditions, which is not a preferable hue for cyan ink. Therefore, when these dyes are used in cyan ink, it is preferable to use them under neutral to alkaline conditions. However, even if the ink is neutral to alkaline, for example, when the recording material is acidic paper, the hue of the recorded matter may change greatly.

In addition, when phthalocyanine dyes are used as cyan ink, the hue of the recorded matter is changed to greenish and decolored by oxidizing gases such as nitrogen oxide gas and ozone, which are often cited as environmental problems. Or, fading or the like also occurs, resulting in a phenomenon that the print density of the recorded matter is lowered.

On the other hand, triphenylmethane dyes are known to have good hues, but are far inferior to phthalocyanine dyes in light resistance, ozone resistance and moisture resistance.

In the future, when the field of use of inkjet recording expands and it is widely used in exhibits such as advertisements, the dyes and inks used therein are light; and oxidizing gases such as ozone gas in the environment; etc. There will be more opportunities for exposure. For this reason, as a cyan dye for inkjet recording, it is more and more desired that it has a good hue, is inexpensive, and is excellent in various fastness properties as described above. However, it is considered difficult to develop cyan dyes and cyan inks that satisfy these requirements at a high level. So far, phthalocyanine dyes imparted with ozone resistance have been disclosed in Patent Documents 3, 8-12, 14-17, etc., but hue, print density, light resistance, ozone resistance, moisture resistance and Cyan dyes that satisfy all qualities, such as not causing bronzing, and can be produced at low cost, have not yet been obtained. 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 International Publication No. 2004/087815 Pamphlet International Publication No. 2002/034844 Pamphlet JP 2004-75986 A International Publication No. 2007/091631 Pamphlet International Publication No. 2007/116933 Pamphlet International Publication No. 2008/111635 Pamphlet

An object of the present invention is to provide a mixture of porphyrazine coloring matter or salt thereof for light cyan ink suitable for ink jet recording having excellent ozone resistance, and an ink composition containing the same.

The inventors of the present invention have studied in detail a dye for light cyan ink having high ozone resistance. As a result, a porphyrazine dye represented by the following formula (1) and having a specific maximum absorption wavelength has the above problem. The inventors have found that this can be solved, and have completed the present invention. That is, the present invention is 1) represented by the following formula (1), and when the measurement of the absorption wavelength using a spectrophotometer in the wavelength range of 400 nm to 800 nm is performed under the following measurement conditions, 598 nm or more A mixture of porphyrazine dyes or salts thereof having a maximum absorption wavelength in the range of 606 nm or less,

[In Formula (1), Rings A to D each independently represent a benzene ring or a pyridine ring fused to a porphyrazine ring, and the average number of pyridine rings is greater than 0.0 and less than or equal to 3.0. Yes, the remainder is a benzene ring, E represents C2-C4 alkylene, X represents an anilino group having a sulfo group, and the anilino group may further have a carboxy group. R ₁ represents a sulfo group, a carboxy group or a hydrogen atom, and a represents an integer of 1 or 2. b is an average value of 0.0 or more and less than 3.9, c is an average value of 0.1 or more and 1.2 or less, and the sum of b and c is an average value of 1.0 or more and 4.0. Is less than. Measurement conditions: An aqueous solution of a dye represented by formula (1) or a salt mixture thereof prepared by adjusting the dye concentration to 0.02 g / liter and pH of 7 to 8, the light source being D65, and the viewing angle Is 2 °, the transmission optical path length is 10 mm, and the temperature of the measurement cell is 25 ° C. In addition, ion-exchange water is used for the preparation of the aqueous solution.

［式（２）中、ｎは平均値で１．０以上４．０未満の数を表す。］、

［（式（３）中、ＥはＣ２−Ｃ４アルキレンを表し、Ｘはスルホ基を有するアニリノ基を表し、該アニリノ基は、さらにカルボキシ基を有しても良い。Ｒ₁はスルホ基、カルボキシ基又は水素原子を表し、ａは１又は２の整数を表す。］、に関する。 2) An ink composition containing 0.1 to 2.5% by mass of a mixture of the porphyrazine coloring matter or salt thereof described in 1) above with respect to the total mass of the ink composition, and 3) further containing a water-soluble organic solvent. The ink composition according to 2) above, 4) the ink composition according to 2) or 3) used for inkjet recording, and 5) the ink composition according to any one of 2) to 4). An ink jet recording method in which recording is performed by ejecting the liquid droplets according to a recording signal and adhering to the recording material, 6) the ink jet recording method according to 5), wherein the recording material is an information transmission sheet, 7) The inkjet recording method according to 6), wherein the information transmission sheet is a surface-treated sheet, and the sheet has an ink image-receiving layer containing white inorganic pigment particles on a support; 8) the 2 4) a container containing the ink composition according to any one of 4), 9) an ink jet printer loaded with the container according to 8), 10) the above 2) to 4). 11) a colored body colored by the ink composition, 11) a colored body colored by the ink jet recording method described in 5), and 12) an ink set having two or more kinds of cyan inks having different dye concentrations, An ink set in which at least one of the cyan inks is the ink composition according to any one of 2) to 4), 13) a compound represented by the following formula (2), and a formula (3) A method for producing a mixture of a porphyrazine dye or a salt thereof according to 1) above, wherein the compound or a salt thereof is reacted in the presence of ammonia,

[In the formula (2), n represents an average value of 1.0 or more and less than 4.0. ],

[(In the formula (3), E represents a C2-C4 alkylene, X represents an anilino group having a sulfo group, said anilino group may further have a carboxy group may .R ₁ is a sulfo group, a carboxy Represents a group or a hydrogen atom, and a represents an integer of 1 or 2.].

A mixture of porphyrazine coloring matter or a salt thereof for light cyan ink suitable for ink jet recording having excellent ozone resistance, and an ink composition containing the same can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. In order to record image or character information on a color display of a computer in color with an ink jet printer, subtractive color mixing with four colors of yellow (Y), magenta (M), cyan (C), and black (K) is generally used. In this way, the recorded image is expressed in color. In order to reproduce the additive color mixture image of red (R), green (G), and blue (B) on a CRT (CRT) display etc. as faithfully as possible with the subtractive color mixture image, each dye used in the ink, especially Y , M, and C are desired to have a hue close to the standard and clear. Here, in addition to the four color inks of Y, M, C, and K described above, it is difficult to express with four colors by using an ink set of four or more colors to which an ink generally called “special color” is added. A method of recording a higher definition image has been proposed. Typical examples of such “spot color” inks include light magenta and light cyan inks.

As a difference between the cyan ink and the light cyan ink, there are some different cyan dyes used for each ink. However, usually the same dye is used, and only the dye content relative to the total mass of each ink is often changed. That is, the same cyan dye is used, and in cyan ink, the cyan dye content is about 5 to 8% by mass relative to the total mass of the ink, and light cyan ink is similarly set to about 1 to 2% by mass. It has been often used for. However, while conventional cyan dyes exhibit excellent fastness in recorded images using cyan ink with a higher dye content, sufficient fastness is achieved when a light cyan ink with a lower dye content is used. It was something that could not demonstrate. For this reason, there is a strong demand for the development of cyan dyes that are excellent in robustness of recorded images when used as light cyan ink. The present invention has found a mixture of a cyan coloring matter or a salt thereof suitable for light cyan ink and an ink composition containing the same, and excellent in fastness, particularly ozone resistance.

Unless otherwise specified, in the following specification, in order to avoid complications, all of the “dye or a mixture of salts thereof” including the whole “dye or a salt thereof” will be simply described as “dye”. The coloring matter of the present invention is a water-soluble coloring matter represented by the above formula (1), that is, a dye, and has a specific maximum absorption wavelength.

The dye represented by the formula (1) will be described.

In the formula (1), rings A to D (four rings A, B, C, and D) represented by broken lines each independently represent a benzene ring or a pyridine ring condensed to a porphyrazine ring. When rings A to D are pyridine rings, the position of the condensed ring to the porphyrazine ring is not particularly limited, but the position of the nitrogen atom constituting the pyridine ring is the 1-position, the 2-position and the 3-position; or the 3-position and Those that are condensed at the 4-position; are preferred. Of these, the latter is more excellent in various fastness properties and tends to have a greenish hue. The number of pyridine rings in Rings A to D is generally an average value of generally greater than 0.0 and 3.0 or less, preferably 0.6 or more and 2.2 or less, more preferably 0.8 or more and 2.0 or less. More preferably, it is 1.0 or more and 1.8 or less. The remaining rings A to D are benzene rings, and all of the benzene rings in rings A to D are usually 1.0 or more and less than 4.0, preferably 1.8 or more and 3.4 or less, more preferably. Is 2.0 or more and 3.2 or less, more preferably 2.2 or more and 3.0 or less. In the present specification, unless otherwise specified, the number of pyridine rings in rings A to D is rounded off to the first digit after the second decimal place. However, for example, when the number of pyridine rings is 1.35 and the number of benzene rings is 2.65, when both are rounded off, the former becomes 1.4 and the latter becomes 2.7, and the sum of both is the sum of rings A to D. 4.0 is exceeded. In such a case, for the sake of convenience, the second digit after the decimal point on the pyridine ring side is rounded down, and only the benzene ring side is rounded off to describe the former as 1.3 and the latter as 2.7. As the number of pyridine rings in the rings A to D increases, the ozone resistance improves, but the bronze phenomenon tends to occur. The number of pyridine rings may be appropriately adjusted in consideration of ozone resistance and the occurrence of bronzing, and a balanced ratio may be selected.

In formula (1), E represents a linear or branched C2-C4 alkylene, and a linear one is preferable. Specific examples include straight chain such as ethylene, propylene and butylene; branched chain such as 2-methylethylene; and the like. Ethylene or propylene is preferable, and ethylene is particularly preferable.

In the formula (1), X represents an anilino group having a sulfo group. The number of sulfo groups is usually 1 to 5, preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 2. The anilino group having a sulfo group in X may further have a carboxy group. In this case, the number of carboxy groups is usually one or two, preferably one. Among these, X preferably has no carboxy group. Specific examples of X include those having one sulfo group such as 2-sulfoanilino, 3-sulfoanilino and 4-sulfoanilino; 2,3-disulfoanilino, 2,4-disulfoanilino, 2,5-disulfoanilino, 3,4-disulfoanilino And those having two sulfo groups such as 3,5-disulfoanilino; those having one sulfo group and one carboxy group such as 2-carboxy-4-sulfoanilino and 2-carboxy-5-sulfoanilino; and the like. Among the specific examples, those having one sulfo group; or those having two sulfo groups are preferable, and 2,5-disulfoanilino is particularly preferable.

In said formula (1), R < ₁ > represents a sulfo group, a carboxy group, or a hydrogen atom. A sulfo group or a hydrogen atom is preferable, and a hydrogen atom is more preferable.

In the formula (1), the substitution position of R ₁ is not particularly limited. The bonding position with “(CH ₂ ) a” is the 1st position, and the substitution position of R is the 2nd position, the 3rd position, or the 4th position, and the 4th position is preferable.

In the formula (1), a represents the number of repetitions of “(CH ₂ )”, that is, the length of alkylene, and is usually an integer of 1 or 2, preferably an integer of 1.

The sum of b, c and b and c in the formula (1) is an average value. b is 0.0 or more and less than 3.9, c is 0.1 or more and less than 1.3, and the sum of b and c is 1.0 or more and less than 4.0 on average. At this time, the average value of the pyridine rings in rings A to D is greater than 0.0 and less than or equal to 3.0, and the benzene ring is 1.0 or more and less than 4.0. Preferably, when the pyridine ring in rings A to D is 0.6 or more and 2.2 or less, and the benzene ring is 1.8 or more and 3.4 or less, b is 0.6 or more and 3.0 or less, and c is 0 4 or more and 1.2 or less, and the sum of b and c is 1.8 or more and 3.4 or less. More preferably, when the pyridine ring in the rings A to D is 0.5 or more and 1.1 or less, the benzene ring is 2.0 or more and 3.2 or less, b is 0.9 or more and 2.7 or less, and c is 0.5 to 1.1 and the sum of b and c is 2.0 to 3.2. More preferably, when the pyridine ring in rings A to D is 1.0 or more and 1.8 or less and the benzene ring is 2.2 or more and 3.0 or less, b is 1.6 or more and 3.0 or less, and c is 0.6 or more and 1.0 or less, and the sum of b and c is 2.2 or more and 3.0 or less. As b increases, ozone resistance tends to improve, but bronzing tends to occur easily. The ratio of b and c may be adjusted as appropriate while considering ozone resistance and the occurrence of bronzing, and a balanced ratio may be selected. 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 pyridine rings, they are not substituted. In this specification, b, c, and the sum of b and c are all rounded off to the first digit by rounding off the second digit after the decimal point. However, as described above for the number of pyridine rings in the rings A to D of the formula (1), the sum of b and c exceeds the number of benzene rings that the unsubstituted sulfamoyl group and the substituted sulfamoyl group can substitute. In this case, the second decimal place of b is rounded down and only c is rounded off.

In the formula (1), in the rings A to D, E, X, R ₁ , a, b, and c, a dye that combines preferable ones is more preferable, and a dye that combines more preferable ones is more preferable. The same applies to preferable combinations, preferable combinations and more preferable combinations.

The manufacturing method of the pigment | dye represented by said Formula (1) is demonstrated. The dye represented by the formula (1) can be obtained by reacting a compound represented by the following formula (2) with a compound represented by the formula (3) in the presence of ammonia. Any of the compounds represented by the following formula (2) can be obtained by synthesizing a compound represented by the following formula (4) according to a known method or according thereto, and then chlorosulfonylating the compound.

In the formula (2), the rings A to D have the same meaning as in the formula (1), including the preferred ones and the preferred number ranges, and n is the sum of b and c in the formula (1). Represents the same meaning.

The compound represented by the following formula (4) can be synthesized, for example, according to a known method disclosed in International Publication No. 2007/091631 and International Publication No. 2007/116933. These known documents do not disclose a production method relating to a compound in which the number of pyridine rings in rings A to D is less than 1. However, when synthesizing by a known nitrile method or Weiler method, the number of pyridine rings in rings A to D can be changed by changing the blending ratio of the pyridine ring dicarboxylic acid derivative used as a reaction raw material and the phthalic acid derivative. A compound represented by the formula (4) in which is less than 1 can also be synthesized. The obtained compound represented by the formula (4) can also be a mixture of positional isomers related to the substitution position of the pyridine ring in rings A to D and the substitution position of the nitrogen atom in the pyridine ring. As described in.

In the formula (4), the rings A to D have the same meaning as in the formula (1) including a preferable number range.

The compound represented by formula (2) is obtained by converting the compound represented by formula (4) to chloroform according to the known method disclosed in the same international pamphlet as in the synthesis of the compound represented by formula (4). It can be obtained by sulfonylation. The chlorosulfonyl group in the formula (2) is introduced on the benzene ring in the rings A to D, and is not introduced when the rings A to D correspond to pyridine rings. Since one chlorosulfonyl group is usually introduced on the benzene ring, the number of n in the formula (2) is within the number of benzene rings in the rings A to D. Therefore, the number “n” of chlorosulfonyl groups in the formula (2) is 1.0 or more and less than 4.0 depending on the number of benzene rings of the compound represented by the formula (2). As another synthesis method of the compound represented by formula (2), a porphyrazine compound having a sulfo group is synthesized by condensing and ring-closing a sulfophthalic acid having a sulfo group and a pyridinedicarboxylic acid derivative such as quinolinic acid in advance. Thereafter, a method of converting the sulfo group into a chlorosulfonyl group with an appropriate chlorinating agent such as thionyl chloride can be mentioned. In this case, the substitution of the sulfo group introduced onto the compound represented by the formula (2) by selecting the substitution position of the sulfo group of the sulfophthalic acid, which is the synthetic raw material, from the 3-position and the 4-position. The position 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 (5), and when 4-sulfophthalic acid is used, it can be selectively introduced at the “β” position. . In the present specification, unless otherwise specified, the term “α-position of the porphyrazine ring” or “β-position of the porphyrazine ring” means a corresponding position in the following formula (5).

The compound represented by the formula (3) or a salt thereof can also be produced by a known method. For example, 0.9 to 1.2 mol of aniline having a sulfo group corresponding to X and 1 mol of 2,4,6-trichloro-S-triazine (cyanuric chloride) are hydroxylated with an alkali metal such as sodium hydroxide. The reaction solution is adjusted to approximately pH 1 to 5 with a product and reacted under conditions of 0 to 40 ° C. and 2 to 12 hours to obtain a primary condensate. Next, 0.9 to 1.5 mol of a compound represented by the following formula (12) is added, and the reaction solution is adjusted to about pH 5 to 10 with an alkali metal hydroxide such as sodium hydroxide, and 5 to 80 A secondary condensate is obtained by reacting at 0.5 ° C. for 0.5 to 12 hours.

In the formula (12), R ₁ represents a sulfo group, a carboxy group or a hydrogen atom, and a represents an integer of 1 or 2.

1 mol of the obtained secondary condensate and 1 to 50 mol of an alkylene diamine corresponding to E (an amine called “H ₂ NE-NH ₂ ”) are about pH 9 to 12, 5 to 90 ° C., 0 The compound represented by the formula (3) is obtained by reacting for 5 to 8 hours. For pH adjustment of each condensation reaction, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; 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 compound represented by the formula (2) and the compound represented by the formula (3) is carried out in a water-containing solvent (preferably water) in the presence of ammonia in the order of pH 8 to 10, 5 to 70 ° C, The reaction is performed for 1 to 20 hours to obtain the porphyrazine coloring matter of the present invention represented by the target 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 compound represented by the formula (3) is usually the theoretical value [the value of c in the dye represented by the target formula (1) is 1 mol per 1 mol of the compound represented by the formula (2). 1 mol or more of the number of moles of the compound represented by the formula (3) necessary for obtaining], but it depends on the reactivity of the organic amine used and the reaction conditions, and is not limited thereto. . Usually, it is about 1 to 3 mol, preferably about 1 to 2 mol of the theoretical value.

Moreover, the pigment | dye represented by the said Formula (1) is synthesize | combined in a water-containing organic solvent (preferably water) from the said Formula (2) and the compound represented by Formula (3). For this reason, a part of the chlorosulfonyl group in formula (2) is hydrolyzed by water present in the reaction system and converted to sulfonic acid as a by-product. It is theoretically conceivable 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 (2) other than the one reacted with the compound represented by the formula (3) Are all 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 dye synthesized by the above-described method can be isolated as a solid by filtration separation or the like from the reaction solution at the final step in the synthesis reaction, by precipitation through acid precipitation or salting out. The salting out is preferably performed in the range of, for example, 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 sodium chloride etc. after heating to 40-80 degreeC normally, Preferably it is 50-70 degreeC.

The dye synthesized by the above method is obtained as a free acid or a salt thereof. Examples of a method for isolating the dye as a free acid include acid precipitation. In addition, as a method of isolating as a salt, when salting out or a desired salt cannot be obtained by salting out, for example, the obtained salt is converted into a free acid, and then a desired organic or inorganic base is added. For example, a known salt exchange method or the like.

Examples of the salt of the dye represented by the formula (1) include salts with inorganic or organic cations. Specific examples of the inorganic cation salt include alkali metal salts such as lithium salts, sodium salts, potassium salts and the like; and ammonium salts (NH ₄ ⁺ ). Examples of the organic cation include, but are not limited to, quaternary ammonium represented by the following formula (13).

In the formula (13), Z ^{1 to} Z ⁴ each independently represent a hydrogen atom, a C1-C4 alkyl group, a hydroxy C1-C4 alkyl group or a hydroxy C1-C4 alkoxy C1-C4 alkyl group, and Z ^{1 to} Z ⁴ At least one of is a group other than a hydrogen atom.

Here, as an example of C1-C4 alkyl group in Z ¹ to Z ⁴ can be mentioned methyl, ethyl and the like. Similarly, examples of hydroxy C1-C4 alkyl groups include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. Similarly, examples of hydroxy C1-C4 alkoxy C1-C4 alkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) butyl, 2- (hydroxyethoxy) Examples include butyl.

Among the salts, preferred are alkali metal salts such as sodium, potassium and lithium; organic quaternary ammonium salts such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine salts And ammonium salts; and the like. Of these, sodium salts, potassium salts, and ammonium salts are more preferable. Of these, sodium salt is particularly preferred.

As is apparent to those skilled in the art, the salt or free acid of the dye represented by the formula (1) can be easily obtained by the following method or the like. For example, in the reaction solution after the final step in the synthesis reaction of the dye represented by the formula (1) or an aqueous solution containing a salt of the dye represented by the formula (1), for example, acetone or C1-C4 alcohol A method of adding a water-soluble organic solvent; a method of salting out by adding sodium chloride; and the like. Can be obtained as Further, after dissolving the obtained sodium salt wet cake in water, an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is separated by filtration, whereby the dye represented by the above formula (1) Or a mixture of free acid and sodium salt in which a part of the dye represented by the formula (1) is a sodium salt. Also, after dissolving the obtained sodium salt wet cake or its dry solid in water, an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added to adjust the pH appropriately, for example, to pH 1 to 3, By separating the precipitated solid by filtration, the ammonium salt of the dye represented by the formula (1) can be obtained. A mixture of the ammonium salt of the dye represented by formula (1) and the sodium salt of the dye represented by formula (1) by appropriately adjusting the amount or / and pH of ammonium chloride to be added; or formula (1) ), A mixture of the free acid of the dye and the ammonium salt; Further, as described later, a free acid solid can be obtained directly by adding a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) to the reaction solution after completion of the reaction. In this case, the wet cake of the free acid of the dye represented by the formula (1) is added to water and stirred, for example, potassium hydroxide; lithium hydroxide; ammonia water; or the organic quaternary formula (13). Ammonium hydroxide; etc. can be added to form a salt to obtain a potassium salt, a lithium salt, an ammonium salt, or a quaternary ammonium salt according to the added compound. By limiting the number of moles of the above-mentioned hydroxide and the like to the number of moles of free acid, for example, a mixed salt of lithium salt and sodium salt, etc .; Etc. can also be prepared. The pigment salt represented by the formula (1) may change the physical properties such as solubility or the performance of the ink when used as an ink depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the intended ink performance.

The dye represented by the formula (1) can be isolated as a solid free acid by adding a mineral acid such as hydrochloric acid after completion of the final step in the synthesis reaction. By washing with water or acidic water such as hydrochloric acid water, inorganic salts (inorganic impurities) contained as impurities, such as sodium chloride and sodium sulfate, can be removed. As described above, the free acid of the compound of the present invention obtained as described above is obtained by treating the obtained wet cake or its dried solid with a desired inorganic or organic base in water to give a salt of the corresponding compound. Solution. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; and ammonium hydroxide (ammonia water). And the like. Examples of the organic base include, but are not limited to, organic amines corresponding to the quaternary ammonium represented by the formula (13), such as alkanolamines such as diethanolamine and triethanolamine.

The pigment | dye represented by Formula (1) obtained as mentioned above melt | dissolves 3-10 mass% with respect to water (Ion-exchange water, distilled water, and a pure water are included) in the dried state. Showing gender.

The dye of the present invention is represented by the above formula (1), and when measurement of absorption wavelength using a spectrophotometer in a wavelength range of 400 nm to 800 nm is performed under specific measurement conditions, 598 nm or more and 606 nm or less. Have a maximum absorption wavelength (hereinafter also referred to as “λmax”). Among these, those having λmax of 600 nm or more and 604 nm or less are particularly preferable in terms of ozone resistance. The specific measurement condition is that an aqueous solution of a mixture of a dye represented by the formula (1) or a salt thereof having a dye concentration adjusted to 0.02 g / liter and a pH of 7 to 8 is prepared. The measurement conditions are D65, the viewing angle is 2 °, the transmission optical path length is 10 mm, and the temperature of the measurement cell is 25 ° C. In addition, ion-exchange water is used for preparation of the dye aqueous solution used for the measurement of absorption wavelength. Note that λmax is obtained by measuring to the first decimal place and rounding off the first decimal place. Even if it is a pigment | dye represented by said Formula (1), when (lambda) max exists in a wavelength shorter than 598 nm, the solubility to water falls extremely, and when using it as an inkjet ink, an increase in ink viscosity etc. will be produced. Therefore, problems such as poor discharge (stability) and clogging of nozzles are likely to occur. On the other hand, those having a wavelength longer than 606 nm tend to have insufficient ozone resistance.

In the above formula (1), the preferable examples for rings A to D, E, X, R ₁ , a, b and c, and the combination of these preferable ones satisfy the range of λmax. Can also be mentioned as preferred and preferred combinations. Further, in the formula (1), those preferred in the rings A to D, E, X, R ₁ , a, b and c, dyes combining these preferred ones, and the like, and the range of the λmax Particularly preferred are dyes in combination with those preferably mentioned for.

The dyes of the present invention are suitable for the dyeing of natural and synthetic fiber materials or blends, as well as for the production of writing inks and inkjet inks. For example, the reaction liquid after completion of the final step in the synthesis reaction of the dye of the present invention can be directly used for the production of the ink composition of the present invention. However, after the reaction liquid or the like is dried by, for example, the above-described method or spray drying, the dye is isolated, and the obtained dye can be processed into an ink composition.

The ink composition of the present invention dissolves the dye of the present invention in water or a mixed solution of water and a water-soluble organic solvent (an organic solvent that can be mixed with water) (also referred to as an aqueous medium). An ink preparation agent is added. When this ink composition is used as an ink for an ink jet printer, a metal cation chloride contained as an impurity, such as sodium chloride; sulfate, such as sodium sulfate; Is preferred. In this case, for example, the total content of sodium chloride and sodium sulfate is about 1% by mass or less with respect to the total mass of the dye of the present invention, and the lower limit may be 0% by mass, that is, below the detection limit of the detection instrument. As a method for producing a compound having a small amount of inorganic impurities, for example, a method using a known reverse osmosis membrane; or a dry product or a wet cake of the compound of the present invention, for example, acetone or C1-C4 alcohol (for example, methanol, ethanol, In addition to a water-soluble organic solvent such as isopropanol or the like, or a water-containing water-soluble organic solvent, suspension purification or crystallization methods, and the like can be mentioned. Desalination treatment or the like may be performed by these methods. The ink composition of the present invention is a water-based ink composition, and the pigment of the present invention is usually 0.1 to 2.5% by mass, preferably 0.3 to 2.0%, based on the total mass of the ink composition. It is contained by mass%, more preferably 0.5 to 1.5 mass%. If necessary, the ink composition of the present invention may further contain a water-soluble organic solvent as long as the effects obtained by the present invention are not impaired. The water-soluble organic solvent is used with the expectation of effects such as dissolution of pigment in the ink composition, prevention of drying, adjustment of viscosity, promotion of penetration, adjustment of surface tension, defoaming, etc. in the ink composition. It is preferable to contain. Examples of the ink preparation agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, ultraviolet absorbers, viscosity adjusting agents, dye dissolving agents, antifading agents, surface tension adjusting agents, antifoaming agents, etc. Known additives may be mentioned. The content of the water-soluble organic solvent is usually 0 to 60% by mass, preferably 10 to 50% by mass, based on the total mass of the ink composition of the present invention; the content of the ink preparation agent is usually 0 to 20% by mass, Preferably it is 0-15 mass%. Moreover, the remainder other than these 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, Amides such as N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido- Heterocyclic ketones such as 2-one; 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 mono- having C2-C6 alkylene units such as 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, or thiodiglycol , Oligo or polyalkylene glycol or thioglycol; polyol (preferably triol) such as trimethylolpropane, 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 Glycol monomethyl ether, C1-C4 monoalkyl ether of polyhydric alcohol such as triethylene glycol monoethyl ether; .gamma.-butyrolactone; or dimethyl sulfoxide and the like.

The water-soluble organic solvent includes substances that are solid at room temperature, such as trimethylolpropane. However, even if the substance or the like is solid, it shows water solubility, and an aqueous solution containing the substance or the like shows the same properties as the water-soluble organic solvent and can be used with the expectation of the same effect. For this reason, in the present specification, for the sake of convenience, even such a solid substance is included in the category of a water-soluble organic solvent as long as it can be used in expectation of the same effect.

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

Examples of the antiseptic / antifungal agent include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8-oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, bromo Indanone-based compounds, benzyl bromacetate-based compounds, and inorganic salt-based compounds are exemplified. 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. Other antiseptic / antifungal agents include sodium acetate, sodium sorbate, sodium benzoate and the like; and trade names Proxel ^RTM GXL (S) and Proxel ^RTM XL-2 (S) manufactured by Arch Chemical Co., respectively. It is done. In the present specification, the superscript “RTM” means a registered trademark.

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

Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil 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 benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds. Further, a compound that absorbs ultraviolet rays typified by a benzoxazole-based compound and emits fluorescence, a so-called fluorescent whitening agent 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. A complex, a zinc complex, etc. are mentioned.

Examples of the surface tension adjusting agent include surfactants, and examples 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, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethylsulfate , Diethylhexyl sulfosuccinate, dioctyl sulfosuccinate and the like.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and other imidazoline derivatives. There is.

Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and other ethers; 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 glycol (alcohol) -based ol; Nissin Chemical Industry Co., Ltd. trade name Surfynol ^RTM 104, 82, 465, Olfine ^RTM STG; SIGMA-ALDRICH Corp. Product Name Tergitol ^RTM 15-S-7;

Examples of antifoaming agents include highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based and silicone-based compounds.

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

In the production of the ink composition of the present invention, there is no particular limitation on the order of dissolving each agent such as an additive. The water used for preparing the ink composition is preferably water with few impurities such as ion exchange water or distilled water. Further, if necessary, after the ink composition is prepared, fine filtration may be performed using a membrane filter or the like to remove impurities in the ink composition. In particular, when the ink composition of the present invention is used as an ink for ink jet recording, it is preferable to perform microfiltration. The pore size of the filter used for microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

The ink composition of the present invention is suitable for use in printing, copying, marking, writing, drawing, stamping, or recording (printing), particularly in inkjet recording. In addition, the ink composition of the present invention is less likely to precipitate a solid even when dried in the vicinity of the nozzles of the recording head of an ink jet printer, and for this reason, the recording head is also less likely to be blocked.

In the ink jet recording method of the present invention, a container filled with the ink composition of the present invention is loaded in a predetermined position of an ink jet printer, and droplets of the ink composition of the present invention are ejected in accordance with a recording signal to be recorded. This is a method of recording by adhering to a material. Some inkjet printers use, for example, a piezo method using mechanical vibration; a bubble jet (registered trademark) method using bubbles generated by heating; and the like. The ink jet recording method of the present invention can be used by any method.

Examples of the recording material used in the inkjet recording method of the present invention include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like. A transmission sheet is preferred. The information transmission sheet is not particularly limited, and a plain paper as well as a surface-treated sheet, specifically, a paper, synthetic paper, a substrate such as a film provided with an ink receiving layer, or the like is used. The ink receiving layer is a layer having an action such as absorbing ink and accelerating its drying. The ink receiving layer is formed by, for example, impregnating or coating the base material with a cationic polymer; or the inorganic fine particles capable of absorbing the pigment in the ink together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone, and the surface of the base material. It is provided by the method of coating to; Examples of the inorganic fine particle material capable of absorbing the pigment in the ink include porous silica, alumina sol, and special ceramics. The information transmission sheet having such an ink-receiving layer is usually called an inkjet exclusive paper, an inkjet exclusive film, a glossy paper, or a glossy film. Typical examples of commercially available information transmission sheets having an ink receiving layer are Canon Inc., trade name Professional Photo Paper, Canon Photographic Paper / Glossy Pro [Platinum Grade], and Glossy Gold; Seiko Epson ( Product name Photo Paper Krispia (high gloss), Photo Paper (Gloss); Nihon Hewlett-Packard Co., Ltd. Product Name Advanced Photo Paper (Gloss); Fuji Film Co., Ltd. Pro; manufactured by Brother Industries, Ltd., trade name: photographic glossy paper BP71G; Also, plain paper means paper that is not particularly provided with an ink receiving layer, and many different types are commercially available depending on the application. Among commercially available plain papers, for ink-jet recording, double-sided fine plain paper (manufactured by Seiko Epson Corporation); PB PAPER GF-500 (manufactured by Canon Inc.); Multipurpose Paper, All-in-one Printing Paper ( Hewlett Packard). In addition, plain paper copy (PPC) paper or the like whose use is not limited to ink jet recording is also plain paper.

The colored body of the present invention means a substance colored with the ink composition of the present invention. The substance to be colored is not particularly limited, and examples thereof include, but are not limited to, the recording material described above. Preferably, the above-mentioned recording material is colored. The coloring method for the substance is not particularly limited, and examples thereof include a printing method such as a dip dyeing method, a textile printing method, and screen printing, and the ink jet recording method of the present invention. The ink jet recording method of the present invention is preferable. Among the colored bodies, a colored body colored by the ink jet recording method of the present invention is preferable.

The ink composition of the present invention can be used as a monochromatic light cyan ink. However, when used in combination with yellow, magenta, cyan, and black inks, it is possible to express a color tone in a wider visible region, which is difficult to express with these four colors. Furthermore, if necessary, it can be used in combination with inks selected from hues such as light magenta, green, red, orange, blue, dark yellow, gray, etc. to express extremely high-definition, for example, photographic images. You can also.

The ink composition containing the dye of the present invention has a dye concentration of 0.1 to 2.5 mass when using at least two kinds of cyan ink as an ink set for the purpose of obtaining a higher-definition recorded image. % Light cyan ink can be suitably used. When used as this ink set, it is preferable to use the ink composition of the present invention for at least one of the ink sets from the viewpoint of fastness and the like, and a known ink (composition) is used for the remaining ink. You may do it.

For the purpose of fine-tuning the hue of the dye of the present invention to a more preferred hue, a mixture of the dye of the present invention is blended with a known cyan dye within a range that does not impair the effects obtained by the present invention. Also good. Examples of known cyan dyes include C.I. I. Direct Blue 86, C.I. I. Direct Blue 87, C.I. I. Direct Blue 199, C.I. I. Acid Blue 9, C.I. I. Acid Blue 249, and C.I. I. Reactive Blue 71 etc. are mentioned. Moreover, you may mix | blend and use the cyan pigment | dye disclosed by patent documents 1-17 similarly.

The ink of the present invention has a clear cyan color, and when used as a light cyan ink, a recorded image having particularly excellent ozone resistance can be obtained. Moreover, it is excellent also in various fastnesses, such as light resistance, water resistance, and moisture resistance, and has the characteristics that it is hard to produce a bronzing phenomenon. Furthermore, the ink composition of the present invention does not precipitate or separate during storage. Further, when the ink according to the present invention is used in ink jet printing, the ejector (ink head) is not blocked. The ink composition of the present invention has physical properties even in a usage environment such as under constant recirculation for a relatively long time when used in a continuous inkjet printer; or intermittent use in an on-demand inkjet printer. Does not cause changes.

EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. Unless otherwise specified, “part” and “%” in the text are based on mass, and the reaction temperature is the internal temperature. In each chemical structural formula of the compounds obtained in the examples, acidic functional groups such as sulfo groups are described in the form of free acids. In addition, "Leocor ^RTM TD-90" used in the examples is a trade name, and is a surfactant manufactured by Lion Corporation.

[Example 1] (Step 1) In the following formula (4), in rings A to D, 1.4 is a pyridine ring fused at the 2-position and 3-position, and the remaining 2.6 is a benzene ring. Synthesis of

To 375 parts of sulfolane, 29.16 parts of phthalic anhydride, 17.23 parts of quinolinic acid, 108 parts of urea, 10.1 parts of copper (II) chloride and 1.5 parts of ammonium molybdate are added, and the temperature is raised to 200 ° C. And reacted at the same temperature for 5 hours. The reaction solution 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 75.1 parts of a wet cake. The obtained wet cake was added to 450 parts of DMF, heated to 110 ° C., and stirred at the same temperature for 1 hour. The solid was separated by filtration and washed with 200 parts of water to obtain a wet cake. 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 solid was separated by filtration and washed with 200 parts of water to obtain a wet cake. The obtained wet cake was added to 450 parts of 5% aqueous ammonia, stirred at 60 ° C. for 1 hour, the solid was separated by filtration and washed with 200 parts of water to obtain 78.6 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 23.1 parts of the target compound as a blue solid.

(Step 2) In the following formula (2), among rings A to D, 1.4 is a pyridine ring condensed at the 2-position and 3-position, the remaining 2.6 is a benzene ring, and n is 2.6. Compound synthesis.

At room temperature, 5.8 parts of the compound of the formula (4) obtained in Example 1 (Step 1) was gradually added to 46.2 parts of chlorosulfonic acid so as not to exceed 60 ° C., and then at 140 ° C. The reaction was performed for 4 hours. The obtained reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was further reacted 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 33.0 parts of the target compound wet cake.

(Step 3) Synthesis of a compound represented by the following formula (10) [compound in which E in the formula (3) is ethylene, X is 2,5-disulfoanilino, a is an integer of ₁ and R ₁ is a hydrogen atom] .

18.4 parts of cyanuric chloride and Leocol ^RTM TD-90 (0.05 parts) were added to 100 parts of ice water, and the mixture was stirred at 10 ° C. or lower for 30 minutes. To this solution, 31.7 parts of 2,5-disulfoaniline (using a commercial product with a purity of 88.4%) was added, and the reaction solution was maintained at pH 2.0 to 3.0 with a 10% aqueous sodium hydroxide solution. The reaction was performed at 0 to 10 ° C. for 2 hours and at 25 to 30 ° C. for 1 hour. 10.9 parts of benzylamine was added to the obtained reaction solution, and the reaction solution was maintained at pH 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution at 25 to 30 ° C. for 1 hour, 30 to 40 ° C. Reaction was performed for a time to obtain a reaction solution. The resulting reaction solution was gradually added to an aqueous solution obtained by adding 60.1 parts of ethylenediamine to 120 parts of ice, and stirred at room temperature for 1 hour. 150 parts of ice and 200 parts of concentrated hydrochloric acid were added to this solution to adjust the pH to 1.0. At this time, the liquid volume was 700 parts. To the obtained liquid, 140 parts of sodium chloride was added and stirred overnight to precipitate a solid. The precipitated solid was separated by filtration to obtain 70.0 parts of a wet cake. The obtained wet cake was added to 280 parts of water, and the solution was adjusted to pH 9.0 with a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 360 parts. This solution was adjusted to pH 1.0 with concentrated hydrochloric acid, 70 parts of sodium chloride was added, and the mixture was stirred overnight to precipitate a solid. The precipitated solid was separated by filtration to obtain 60.3 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 solid was separated by filtration to obtain 50.3 parts of a wet cake. The obtained wet cake was dried to obtain 15.3 parts of the objective compound as a white powder. (Step 4) Dye of the present invention represented by the following formula (11) [Pyridine ring in which 1.4 of rings A to D in formula (1) is fused at the 2-position and 3-position, the remaining 2.6 Is a benzene ring, E is ethylene, X is 2,5-disulfoanilino, a is an integer of ₁ , R ₁ is a hydrogen atom, b is 1.8, and c is 0.8.

A solution was prepared by dissolving 3.71 parts of the compound of the formula (10) obtained in Example 1 (Step 3) in a mixed solution of 1 part of 28% aqueous ammonia and 40 parts of water. On the other hand, 33.0 parts of the wet cake obtained in Example 1 (Step 2) was added to 100 parts of ice water, and suspended by stirring at 5 ° C. or lower for 10 minutes. To this solution, a solution containing the compound of formula (10) prepared above was added at 10 ° C. or less, and reacted for 0.5 hours while maintaining the reaction solution at pH 9.0 with 28% aqueous ammonia. While maintaining the same pH, the temperature of the reaction solution was raised to 20 ° C. and further reacted at the same temperature overnight. 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, the pH was adjusted to 7.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and washed with 100 parts of a 20% aqueous sodium chloride solution. , 124.3 parts of a wet cake was obtained. The obtained wet cake was added to 100 parts of water, and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 250 parts. The solution was heated to 50 ° C., 50 parts of sodium chloride was added and stirred for 30 minutes, adjusted to pH 7.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and washed with 100 parts of a 10% aqueous sodium chloride solution. , 54.5 parts of a wet cake was obtained. The obtained wet cake was added to 150 parts of water, and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 250 parts. The solution was heated to 50 ° C., 12.5 parts of sodium chloride was added and stirred for 30 minutes, then adjusted to pH 1.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and 100 parts of 5% aqueous sodium chloride solution was added. Washing gave 76.3 parts of a wet cake. The obtained wet cake was added to a mixed liquid of 320 parts of isopropyl alcohol and 80 parts of water and stirred at 50 ° C. for 1 hour, and the solid was filtered and separated to obtain 32.1 parts of a wet cake. The obtained wet cake was dried to obtain 9.1 parts of the desired free acid of the dye of the present invention as a blue powder. λmax: 602 nm.

[Example 2] Porphyrazine dye of the present invention represented by the above formula (11) [Pyridine ring fused with 1.4 in the 2nd and 3rd positions among the rings A to D in the above formula (1), remaining 2.6 is a benzene ring, E is ethylene, X is 2,5-disulfoanilino, a is an integer of ₁ , R ₁ is a hydrogen atom, b is 1.6, and c is 1.0. Synthesis. 4.95 parts of the compound of the formula (10) obtained in Example 1 (Step 3) was dissolved in a mixed solution of 1 part of 28% aqueous ammonia and 40 parts of water to prepare a solution. On the other hand, 33.0 parts of a wet cake obtained in the same manner as in Example 1 (Step 2) was added to 100 parts of ice water, and the mixture was suspended by stirring at 5 ° C. or lower for 10 minutes. To this solution, a solution containing the compound of formula (10) prepared above was added at 10 ° C. or less, and reacted for 0.5 hours while maintaining the reaction solution at pH 9.0 with 28% aqueous ammonia. While maintaining the same pH, the temperature of the reaction solution was raised to 20 ° C. and further reacted at the same temperature overnight. 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, the pH was adjusted to 7.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and washed with 100 parts of a 20% aqueous sodium chloride solution. , 104.3 parts of a wet cake was obtained. The obtained wet cake was added to 230 parts of water, and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 375 parts. The solution was heated to 50 ° C., 18.7 parts of sodium chloride was added and stirred for 30 minutes, then adjusted to pH 3.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and 100 parts of 5% aqueous sodium chloride solution was added. Washing gave 54.5 parts of wet cake. The obtained wet cake was added to a mixed solution of 320 parts of isopropyl alcohol and 80 parts of water and stirred at 50 ° C. for 1 hour, and the solid was separated by filtration to obtain 38.8 parts of a wet cake. The obtained wet cake was dried to obtain 10.3 parts of the desired free acid of the dye of the present invention as a blue powder. λmax: 604 nm. [Example 3] Porphyrazine dye of the present invention represented by the above formula (11) [Pyridine ring in which 1.4 of the rings A to D in the above formula (1) are condensed at the 2-position and 3-position, and the rest 2.6 is a benzene ring, E is ethylene, X is 2,5-disulfoanilino, a is an integer of ₁ , R ₁ is a hydrogen atom, b is 1.8, and c is 0.8. Synthesis. A solution was prepared by dissolving 3.71 parts of the compound of the formula (10) obtained in Example 1 (Step 3) in a mixed solution of 1 part of 28% aqueous ammonia and 40 parts of water. On the other hand, 33.0 parts of a wet cake obtained in the same manner as in Example 1 (Step 2) was added to 100 parts of ice water, and the mixture was suspended by stirring at 5 ° C. or lower for 10 minutes. To this solution, a solution containing the compound of formula (10) prepared above was added at 10 ° C. or less, and reacted for 0.5 hours while maintaining the reaction solution at pH 9.0 with 28% aqueous ammonia. While maintaining the same pH, the temperature of the reaction solution was raised to 20 ° C. and further reacted at the same temperature overnight. 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, the pH was adjusted to 7.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and washed with 100 parts of a 20% aqueous sodium chloride solution. , 124.3 parts of a wet cake was obtained. The obtained wet cake was added to 100 parts of water, and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 250 parts. The solution was heated to 50 ° C., 50 parts of sodium chloride was added and stirred for 30 minutes, adjusted to pH 7.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and washed with 100 parts of a 10% aqueous sodium chloride solution. , 54.5 parts of a wet cake was obtained. The obtained wet cake was added to 100 parts of water and adjusted to pH 9.0 with a 25% aqueous potassium hydroxide solution to obtain a solution. The liquid volume at this time was 250 parts. This solution was heated to 50 ° C., 25 parts of potassium chloride was added and stirred for 30 minutes, then adjusted to pH 1.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and washed with 100 parts of a 10% aqueous potassium chloride solution. To obtain 71.3 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% aqueous potassium hydroxide solution to obtain a solution. The liquid volume at this time was 300 parts. The solution was heated to 50 ° C., 15 parts of potassium chloride was added and stirred for 30 minutes, then adjusted to pH 1.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and washed with 100 parts of a 1% aqueous potassium chloride solution. , 62.2 parts of a wet cake was obtained. The obtained wet cake was added to a mixed liquid of 320 parts of isopropyl alcohol and 80 parts of water and stirred at 50 ° C. for 1 hour, and the solid was filtered and separated to obtain 32.1 parts of a wet cake. The obtained wet cake was dried to obtain 9.6 parts of the target free acid of the dye of the present invention as a blue powder. λmax: 600 nm. [Example 4] (Step 1) Among the rings A to D in the formula (4), 0.7 is a pyridine ring condensed at the 2-position and 3-position, and the remaining 3.3 is a benzene ring. Synthesis.

To 375 parts of sulfolane, 36.1 parts of phthalic anhydride, 9.4 parts of quinolinic acid, 108 parts of urea, 10.1 parts of copper (II) chloride and 1.5 parts of ammonium molybdate are added, and the temperature is raised to 200 ° C. And reacted at the same temperature for 5 hours. The reaction solution 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 75.1 parts of a wet cake. The obtained wet cake was added to 450 parts of DMF, heated to 110 ° C., and stirred at the same temperature for 1 hour. The solid was separated by filtration and washed with 200 parts of water to obtain a wet cake. 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 solid was separated by filtration, and washed with 200 parts of water to obtain a wet cake. The obtained wet cake was added to 450 parts of 5% aqueous ammonia, stirred at 60 ° C. for 1 hour, the solid was separated by filtration and washed with 200 parts of water to obtain 78.6 parts of a wet cake. The obtained wet cake was dried to obtain 32.6 parts of the target compound as a blue solid.

(Step 2) A compound in which 0.7 is a pyridine ring condensed at the 2-position and 3-position among the rings A to D in the formula (2), the remaining 3.3 is a benzene ring, and n is 3.3 Synthesis of

After gradually adding 5.8 parts of the compound of the formula (4) obtained in Example 4 (Step 1) to 46.2 parts of chlorosulfonic acid at room temperature so as not to exceed 60 ° C., 140 ° C. The reaction was performed for 4 hours. The obtained reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was further reacted 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 32.2 parts of the target compound wet cake.

(Step 3) Porphyrazine dye of the present invention represented by the above formula (11) [Pyridine ring in which 0.7 of the rings A to D in the above formula (1) is condensed at the 2nd and 3rd positions, the remaining 3 .3 is a benzene ring, E is ethylene, X is 2,5-disulfoanilino, a is an integer of ₁ , R ₁ is a hydrogen atom, b is 2.5, and c is 0.8. . A solution was prepared by dissolving 3.71 parts of the compound of the formula (10) obtained in Example 1 (Step 3) in a mixed solution of 2 parts of 28% aqueous ammonia and 30 parts of water. On the other hand, 32.2 parts of a wet cake obtained in the same manner as in Example 1 (Step 2) was added to 100 parts of ice water, and the suspension was stirred and suspended at 5 ° C. or lower for 10 minutes. A solution containing the compound of the formula (10) prepared previously was added to this solution at 10 ° C. or lower, and reacted for 10 hours while maintaining the reaction solution at pH 9.0 with 28% aqueous ammonia. While maintaining the same pH, the temperature of the reaction solution was raised to 20 ° C. and further reacted at the same temperature overnight. 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 10 minutes, and then adjusted to pH 7.0 with concentrated hydrochloric acid. The precipitated solid was separated by filtration and washed with 200 parts of a 20% aqueous sodium chloride solution to obtain 65.3 parts of a wet cake. To the obtained wet cake, 200 parts of water was added and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 300 parts. This solution was heated to 50 ° C., 15 g of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid. The precipitated solid was separated by filtration and washed with 100 parts of a 5% aqueous sodium chloride solution to obtain 53.5 parts of a wet cake. The obtained wet cake was added to a mixed solution of 64 parts of water and 256 parts of isopropyl alcohol, stirred at 50 ° C. for 1 hour, and the solid was separated by filtration to obtain 27.8 parts of a wet cake. The obtained wet cake was dried to obtain 10.4 parts of the desired free acid of the dye of the present invention as a blue powder. λmax: 606 nm.

[Comparative Example 1] (Step 1) Comparative porphyrazine dye represented by the formula (11) [0.7 of the rings A to D in the formula (1) were condensed at the 2-position and 3-position. A pyridine ring, the remaining 3.3 is a benzene ring, E is ethylene, X is 2,5-disulfoanilino, a is an integer of ₁ , R ₁ is a hydrogen atom, b is 1.8, and c is 1.5] Synthesis of. 7.4 parts of the compound of the formula (10) obtained in Example 1 (Step 3) was dissolved in a mixed solution of 2 parts of 28% aqueous ammonia and 30 parts of water to prepare a solution. On the other hand, 32.2 parts of a wet cake obtained in the same manner as in Example 1 (Step 2) was added to 100 parts of ice water, and the suspension was stirred and suspended at 5 ° C. or lower for 10 minutes. To this solution, a solution containing the compound of formula (10) prepared above was added at 10 ° C. or less, and reacted for 0.5 hours while maintaining the reaction solution at pH 9.0 with 28% aqueous ammonia. While maintaining the same pH, the temperature of the reaction solution was raised to 20 ° C. and further reacted at the same temperature overnight. 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 10 minutes, and then adjusted to pH 4.5 with concentrated hydrochloric acid. The precipitated solid was separated by filtration and washed with 200 parts of a 20% aqueous sodium chloride solution to obtain 42.8 parts of a wet cake. To the obtained wet cake, 200 parts of water was added and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 260 parts. This solution was heated to 50 ° C., 50 g of sodium chloride was added and stirred for 30 minutes, and then the precipitated solid was separated by filtration and washed with 200 parts of a 20% aqueous sodium chloride solution to obtain 36.24 parts of a wet cake. To the obtained wet cake, 200 parts of water was added and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 250 parts. This solution was heated to 50 ° C., 12.5 g of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid. The precipitated solid was separated by filtration and washed with 100 parts of a 5% aqueous sodium chloride solution to obtain 41.4 parts of a wet cake. The obtained wet cake was added to a mixed solution of 40 parts of water and 160 parts of isopropyl alcohol and stirred at 50 ° C. for 1 hour, and then the solid was separated by filtration to obtain 31.3 parts of a wet cake. The obtained wet cake was dried to obtain 12.5 parts of a free acid of a target comparative pigment as a blue powder.

[Comparative Example 2] (Step 1) Synthesis of a compound represented by the following formula (24).

To 750 parts of sulfolane, 320.0 parts of 4-sulfophthalic acid (using a commercially available product containing 20% 3-sulfophthalic acid and obtained as a 50% aqueous solution) and 47.3 parts of 28% aqueous ammonia were added, and the temperature was increased to 160 ° C. The temperature was raised and the reaction was carried out at the same temperature for 2 hours. Thereafter, the mixture is cooled to 65 ° C., 25.1 parts of quinolinic acid, 288 parts of urea, 36.4 parts of copper (II) acetate and 4 parts of ammonium molybdate are added, and the temperature is raised again to 200 ° C., and the same temperature is maintained for 5 hours. Reacted. After completion of the reaction, the mixture was cooled to 90 ° C., 180 parts of 35% hydrochloric acid was added, and the mixture was stirred at 90 ° C. for 1 hour. 440 parts of methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was washed with 400 parts of methanol to obtain 531 parts of a wet cake. A wet cake obtained in a mixed solution of 184.8 parts of water and 40.2 parts of 35% hydrochloric acid was added, the temperature was raised to 60 ° C., and the mixture was stirred at the same temperature for 1 hour to obtain a solution. 60 parts of methanol and 500 parts of 2-propanol were added to the obtained liquid, and the precipitated solid was separated by filtration and washed with 400 parts of 20% water-containing 2-propanol to obtain a wet cake. The obtained wet cake was added to a mixed solution of 28 parts aqueous ammonia (106 parts) and methanol (750 parts), heated to 60 ° C., and stirred at the same temperature for 1 hour. The solid was separated by filtration and washed with 400 parts of methanol to obtain 361 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 142.1 parts of the target compound represented by the formula (24) as a blue solid.

(Step 2) Synthesis of a compound represented by the following formula (25).

After gradually adding 8.9 parts of the compound of the formula (24) obtained in Comparative Example 2 (Step 1) to 53.2 parts of chlorosulfonic acid at room temperature so as not to exceed 60 ° C., The temperature was raised to 120 ° C. and reacted for 4 hours. The obtained reaction solution was cooled to 70 ° C., 25.0 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was further reacted at 80 ° 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 40.1 parts of the target compound wet cake.

(Step 3) A porphyrazine dye for comparison represented by the formula (11) [a pyridine ring in which 0.7 of the rings A to D in the formula (1) is condensed at the 2-position and 3-position, the remaining 3 .3 is a benzene ring, E is ethylene, X is 2,5-disulfoanilino, a is an integer of ₁ , R ₁ is a hydrogen atom, b is 2.0, and c is 1.3.

A solution was prepared by dissolving 6.2 parts of the compound of the formula (10) obtained in Example 1 (Step 3) in a mixed solution of 2 parts of 28% aqueous ammonia and 30 parts of water. On the other hand, 40.1 parts of the wet cake obtained in Comparative Example 2 (Step 2) was added to 100 parts of ice water, and suspended by stirring at 5 ° C. or lower for 10 minutes. A solution containing the compound of formula (10) prepared earlier was added to this solution at 10 ° C. or less, and reacted for 0.5 hours while maintaining the reaction solution at pH 8.0 with 28% aqueous ammonia. While maintaining the same pH, the temperature of the reaction solution was raised to 20 ° C. and further reacted at the same temperature overnight. 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 10 minutes, and then adjusted to pH 5.0 with concentrated hydrochloric acid. The precipitated solid was separated by filtration and washed with 200 parts of a 20% aqueous sodium chloride solution to obtain 30.1 parts of a wet cake. To the obtained wet cake, 200 parts of water was added and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 250 parts. This solution was heated to 50 ° C., 25 g of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 4.0 with concentrated hydrochloric acid. The precipitated solid was separated by filtration and washed with 100 parts of a 10% aqueous sodium chloride solution to obtain 45.3 parts of a wet cake. To the obtained wet cake, 200 parts of water was added and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 300 parts. This solution was heated to 50 ° C., 15 g of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid. The precipitated solid was separated by filtration and washed with 100 parts of a 5% aqueous sodium chloride solution to obtain 59.4 parts of a wet cake. The obtained wet cake was added to a mixed solution of 64 parts of water and 256 parts of isopropyl alcohol and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 28.1 parts of a wet cake. The obtained wet cake was dried to obtain 11.6 parts of a free acid for comparison purposes as a blue powder.

(A) Preparation of light cyan ink [Examples 5 to 8] The components described in Table 1 below were mixed and dissolved, and filtered through a 0.45 μm membrane filter (manufactured by Advantech) to obtain a test ink. . The water used was ion exchange water. Further, water and a 12.5% aqueous sodium hydroxide solution were appropriately added so that the pH of the ink was 8 to 10 and the total amount was 100 parts. Preparation of ink using the mixture of pigments obtained in Example 1 is Example 5, and preparation of ink using the mixture of pigments obtained in Examples 2 to 4 is respectively Example 6 to 8. However, in Example 7 using the mixture of dyes obtained in Example 3, the pH was adjusted using 12.5% aqueous potassium hydroxide instead of 12.5% aqueous sodium hydroxide. . In Table 1 below, “surfactant” manufactured by Nissin Chemical Co., Ltd., trade name Surfinol ^RTM 104PG50 was used.

[Comparative Examples 3 and 4] A light cyan ink for comparison was prepared in the same manner as in Example 5 except that the mixture of dyes synthesized in Comparative Example 1 or 2 was used instead of the mixture of dyes synthesized in each Example. Each was prepared. The ink preparation using the mixture of pigments synthesized in Comparative Example 1 is referred to as Comparative Example 3, and the ink preparation using the mixture of pigments synthesized in Comparative Example 2 is referred to as Comparative Example 4.

(B) Inkjet recording Two types of glossy papers (A) and (B) described below using the inks prepared in each Example and Comparative Example using an inkjet printer (product name PIXUS ^RTM ip4500, manufactured by Canon Inc.) Inkjet recording was performed.

Glossy paper (A): Photographic paper crispia (glossy), manufactured by Seiko Epson Corporation. Glossy paper (B): Photographic paper, glossy professional platinum grade, manufactured by Canon Inc.

  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, the print density (Dc) of the recorded matter before the test was measured, and the dye residual ratio in the gradation portion closest to Dc = 1.0 was determined. The reflection density was measured using a color measurement system (product name: SpectroEye, manufactured by X-rite). 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] Each test piece was measured using an ozone weather meter (Suga Test Instruments Co., Ltd., model OMS-H) with an ozone concentration of 12 ppm, a bath temperature of 23 ° C, and a humidity of 50% RH. Left for 24 hours. For each test piece, the reflection density before and after the test is measured using the above-described colorimetry system, and the residual ratio of the dye is calculated by (reflection density after test / reflection density before test) × 100 (%). It was. The measured values of the test results are shown in Table 2 below.

(D) Measurement of maximum absorption wavelength (λmax) The maximum absorption wavelength of each dye mixture synthesized in Examples 1 to 4 and Comparative Examples 1 to 3 was measured by the following method. (D-1) Preparation of sample for measurement After weighing 0.1 g of each dye mixture and adding 0.1 g of 12.5% aqueous sodium hydroxide solution to make a solution, ion-exchanged water was added to a 500 ml volumetric flask. The solution was transferred while washing, and ion-exchanged water was further added to prepare a 500 ml aqueous solution. 10 ml from the obtained aqueous solution was collected with a whole pipette, transferred to a 100 ml measuring flask, and ion exchanged water was added to prepare a 100 ml aqueous solution, whereby the dye concentration was 0.02 g / liter and the pH was Samples for measuring the maximum absorption wavelength, 7 to 8, were prepared. (D-2) Measuring method of absorption wavelength Each sample obtained in the above (D-1) is a spectrophotometer UV-2550 manufactured by SHIMADZU according to a conventional method, the light source is D65, the viewing angle is 2 °, The absorption wavelength in the wavelength range of 400 nm to 800 nm was measured under conditions where the transmission optical path length was 10 mm and the temperature of the measurement cell was 25 ° C. The measurement results are shown in Table 2 below.

As is apparent from the results in Table 2, each example having the maximum absorption wavelength in the range of 598 nm to 606 nm exhibits excellent ozone resistance with respect to each comparative example having no maximum absorption wavelength in this range. Was confirmed. In each of the examples, those having the maximum absorption wavelength in the range of 600 nm to 604 nm are particularly excellent in ozone resistance and are extremely useful as light cyan ink.

[Example 9] (Step 1) Among the rings A to D in the formula (4), 1.2 is a pyridine ring condensed at the 2-position and 3-position, and the remaining 2.8 is a benzene ring. Synthesis.

To 375 parts of sulfolane, 31.11 parts of phthalic anhydride, 15.04 parts of quinolinic acid, 108 parts of urea, 10.1 parts of copper (II) chloride and 1.5 parts of ammonium molybdate are added, and the temperature is raised to 200 ° C. And reacted at the same temperature for 5 hours. The reaction solution was cooled to 65 ° C., 50 parts of DMF was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 50 parts of DMF to obtain 75.1 parts of a wet cake. The obtained wet cake was added to 450 parts of DMF, heated to 110 ° C., and reacted at the same temperature for 1 hour. The solid precipitated from this reaction solution was separated by filtration and washed with 200 parts of water to obtain a wet cake. 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 solid precipitated from the obtained liquid was separated by filtration and washed with 200 parts of water to obtain a wet cake. The obtained wet cake was added to 450 parts of 5% aqueous ammonia and stirred at 60 ° C. for 1 hour. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain 78.6 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 24.9 parts of the target compound as a blue solid.

(Step 2) Compound in which 1.2 of rings A to D in formula (2) is a pyridine ring condensed at the 2-position and 3-position, the remaining 2.8 is a benzene ring, and n is 2.8 Synthesis of

After gradually adding 5.8 parts of the compound of the formula (4) obtained in Example 9 (Step 1) to 46.2 parts of chlorosulfonic acid at room temperature so as not to exceed 60 ° C., 140 ° C. The reaction was performed for 4 hours. The obtained reaction solution was cooled to 70 ° C., and 17.9 parts of thionyl chloride was added dropwise to the solution over 30 minutes, followed by further reaction at 70 ° C. for 3 hours. The reaction solution was cooled to 30 ° C. or lower and then slowly poured into 800 parts of ice water, and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was washed with 200 parts of cold water to obtain 38.2 parts of the target compound wet cake.

(Process 3)
The porphyrazine dye of the present invention represented by the above formula (11) [1.2 in ring A to D in the formula (1) is a pyridine ring condensed at the 2-position and 3-position, and the remaining 2.8 is benzene Ring, E is ethylene, X is 2,5-disulfoanilino, a is an integer of 1, group F is phenyl, and R is a hydrogen atom].

38.2 parts of the wet cake obtained in Example 9 (Step 2) was added to 200 parts of ice water and suspended by stirring at 5 ° C. or lower. After 10 minutes, while maintaining the temperature at 10 ° C. or lower, 3.7 parts of the organic amine of the formula (10) obtained in Example 1 (Step 3) was mixed into a mixed solution of 1.5 parts of 28% aqueous ammonia and 40 parts of water. The dissolved solution was added to this suspension and reacted overnight while maintaining pH 9.0 with 28% aqueous ammonia. While maintaining the pH of the obtained liquid at 9.0, the temperature was raised to 20 ° C., and the mixture was further reacted overnight at the same temperature. The liquid volume at this time was 250 parts. The temperature of the reaction solution was raised to 50 ° C., 50 parts of sodium chloride was added and stirred for 30 minutes, the solution was adjusted to pH 5.0 with concentrated hydrochloric acid, and the precipitated solid was separated by filtration. The obtained solid was washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 24.2 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% aqueous sodium hydroxide solution to obtain a solution. The liquid volume at this time was 250 parts. The temperature of this solution was raised to 50 ° C., 50 parts of sodium chloride was added and stirred for 30 minutes, then this solution was adjusted to pH 5.0 with concentrated hydrochloric acid, and the precipitated solid was separated by filtration. The obtained solid was washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 20.1 parts of a wet cake. The obtained wet cake was added to a mixed liquid of 340 parts of methanol and 60 parts of water to form a suspension, and after stirring at 50 ° C. for 1 hour, the solid was separated by filtration to obtain 13.9 parts of a wet cake. The obtained wet cake was dried to obtain 10.8 parts of a free acid of the dye of the present invention represented by the formula (11) as a blue powder. λmax: 602 nm. A light cyan ink was prepared in the same manner as in Examples 5 to 8 using the obtained dye of the present invention, and (C) evaluation of a recorded image [ozone resistance test] was performed. As a result, the light cyan ink using the pigment obtained in Example 9 (Step 3) also showed ozone resistance equivalent to that in Examples 5 to 8.

  The porphyrazine coloring matter or a mixture thereof and the ink composition containing the same of the present invention are extremely suitable as a light cyan ink for various recordings, particularly for inkjet recording.

Claims (13)

When the measurement of the absorption wavelength using the spectrophotometer in the wavelength range of 400 nm to 800 nm represented by the following formula (1) is performed under the following measurement conditions, the maximum absorption wavelength is in the range of 598 nm to 606 nm. A mixture of porphyrazine dyes or salts thereof having

[In Formula (1), Rings A to D each independently represent a benzene ring or a pyridine ring fused to a porphyrazine ring, and the average number of pyridine rings is greater than 0.0 and less than or equal to 3.0. Yes, the remainder is a benzene ring, E represents C2-C4 alkylene, X represents an anilino group having a sulfo group, and the anilino group may further have a carboxy group. R ₁ represents a sulfo group, a carboxy group or a hydrogen atom, and a represents an integer of 1 or 2. b is an average value of 0.0 or more and less than 3.9, c is an average value of 0.1 or more and 1.2 or less, and the sum of b and c is an average value of 1.0 or more and 4.0. Is less than. ]. Measurement conditions: An aqueous solution of a mixture of a dye represented by formula (1) or a salt thereof adjusted to a dye concentration of 0.02 g / liter and a pH of 7 to 8 is prepared, the light source is D65, and the viewing angle is 2 The measurement is performed at a temperature of 10 mm and a measurement cell temperature of 25 ° C. In addition, ion-exchange water is used for preparation of this aqueous solution. An ink composition comprising 0.1 to 2.5% by mass of the mixture of the porphyrazine coloring matter or a salt thereof according to claim 1 with respect to the total mass of the ink composition. The ink composition according to claim 2, further comprising a water-soluble organic solvent. The ink composition according to claim 2 or 3 used for inkjet recording. An ink jet recording method for performing recording by ejecting droplets of the ink composition according to any one of claims 2 to 4 in accordance with a recording signal and attaching the droplets to a recording material. The ink jet recording method according to claim 5, wherein the recording material is an information transmission sheet. The ink jet recording method according to claim 6, wherein the information transmission sheet is a surface-treated sheet and has an ink image-receiving layer containing white inorganic pigment particles on a support. A container containing the ink composition according to any one of claims 2 to 4. An ink jet printer loaded with the container according to claim 8. The colored body colored with the ink composition as described in any one of Claims 2 thru | or 4. A colored body colored by the ink jet recording method according to claim 5. An ink set having two or more types of cyan inks having different pigment concentrations, wherein at least one of the cyan inks is the ink composition according to any one of claims 2 to 4. The porphyrazine coloring matter or a mixture of salts thereof according to claim 1, wherein the compound represented by the following formula (2) is reacted with a compound represented by the following formula (3) or a salt thereof in the presence of ammonia. Production method,

[In the formula (2), n represents an average value of 1.0 or more and less than 4.0. ],

[(In the formula (3), E represents a C2-C4 alkylene, X represents an anilino group having a sulfo group, said anilino group may further have a carboxy group may .R ₁ is a sulfo group, a carboxy Represents a group or a hydrogen atom, and a represents an integer of 1 or 2.]