JP2005320480A - Anthrapyridone compound, aqueous ink containing the same, and inkjet recording method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anthrapyridone type aqueous coloring matter compound which has the color developing nature in the violet or blue color region and which is suitable for preparing an aqueous ink excellent in the color developing nature and the fastness of images (lightfastness and resistance to gases) suited to inkjet recording, and to provide an ink using this. <P>SOLUTION: The anthrapyridone compound is the one in which the form of its free acid is represented by general formula (I). The aqueous ink is what contains this anthrapyridone compound as the coloring matter component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dye compound (coloring material) that can be suitably used for ink jet recording, an ink for ink jet recording, and an ink jet recording method. More specifically, the present invention relates to a novel anthrapyridone compound, and a purple to blue aqueous ink containing the compound ( The present invention relates to an ink) and an ink jet image forming method using the same.

  The ink jet recording method is a method for recording images, characters, and the like by ejecting micro droplets of ink by various operating principles and attaching them to a recording medium (paper, etc.). It has features such as easy, high flexibility of recording patterns, no need for development and fixing, and is rapidly spreading in various applications. In recent years, in particular, due to the miniaturization of ejected droplets, the use of dark and light inks, and the improvement of image processing technology, the image quality of images obtained by inkjet recording methods has reached a level comparable to images obtained by conventional silver salt methods. ing.

  In addition to the conventionally used yellow, magenta, cyan, and black, as a means for further improving the image quality, an ink jet recording type color printer that uses so-called special color inks such as orange, green, and blue is a large format. It is marketed in the field of textile printing. Color materials for special color inks used in the above-mentioned fields are pigments or reactive dyes.

  However, these color materials exhibit good color developability on a specific recording medium, and the formed image can have good fastness such as light resistance and gas resistance. On the recording medium such as glossy paper for inkjet, glossy film, matte coated paper, coated paper, plain paper, OHP film, etc. used for printing the photo image obtained in the above, good color development, light resistance and light resistance. It was not a color material satisfying both high image fastness in gas properties and the like.

  That is, when a pigment is used, the image fastness is sufficient, but regarding color developability, an image having excellent color developability cannot be obtained unless the recording medium is specially prepared for the pigment. Even with a special recording medium, the glossiness of the image was inferior to that when a dye was used. Furthermore, as a problem of glossiness of the image when using pigment ink, the difference in glossiness between the image forming portion where the pigment is present on the recording medium and the non-image forming portion is also an ink jet formed with the dye ink. It becomes a problem when a high image quality equivalent to that of a photo image is required.

  On the other hand, a reactive dye used in the textile printing field is one in which a dye image is fixed on a cloth for the first time after printing on a textile for printing and by combining the dye and the cloth by post-treatment such as steaming. It is extremely difficult to mount the printer on consumer printers. What has been described above is a problem when a conventionally known color material for special color is used when printing a photo image.

  As for the water-soluble dye technology that is currently used in many ink jet printers, a conventionally known blue dye, which is a dye having color developability in the purple to blue color gamut targeted by the present invention, is, for example, , C.I. I. Acid Blue 62, 80, 90, 104, 112, 203, 204 and the like can be mentioned, but all of them have a problem in image robustness. That is, the image formed when these dyes were used was extremely poor in both light resistance and gas resistance, or any of them, and could not be used.

  Therefore, if the above-described problems of the prior art are solved and an ink that can achieve both good color development and high image fastness (light resistance, gas resistance) without limiting the recording medium can be realized. Very useful. Among such inks, inks having color developability in the purple to blue region are particularly useful. For this purpose, development of an aqueous coloring compound (coloring material) that can be suitably used for the ink is desired. Here, the purple to blue region in the present invention means the hue (Hue) of the region of 270 ≦ h ≦ 315 in the LCh color system.

  In response to the above-described problems, a basic skeleton candidate of a purple dye compound that can be used to prepare an ink having color developability in the purple to blue region and has both excellent color developability and image fastness (light resistance, gas resistance). Examples thereof include an anthrapyridone type (see, for example, Patent Documents 1 and 2). However, when it is used for ink, an image satisfying all of hue, sharpness, image fastness (light resistance, gas resistance) and ink dissolution stability has not been obtained.

JP 59-74173 A JP-A-2-16171

  Accordingly, an object of the present invention is a water-based ink having a color development property in a purple to blue region (hereinafter also referred to as a blue region) and excellent in color development property suitable for ink jet recording and image fastness (light resistance, gas resistance). It is to provide an anthrapyridone-based aqueous dye compound that can be suitably used in preparing the above. Another object of the present invention is to provide an ink that has excellent color developability in the blue region, and that the obtained image is excellent in image fastness such as light resistance and gas resistance. Furthermore, an object of the present invention is to provide an ink jet recording method capable of obtaining an image excellent in color development in a blue region and having excellent image fastness such as light resistance and gas resistance.

（式中、Ｒ₁は水素原子、アルコキシカルボニル基、及びベンゾイル基から選ばれる何れかを示し、Ｒ₂は、水素原子又はアルキル基を示す。） As a result of intensive studies to solve the problems as described above, the present inventors have reached the present invention. That is, the present invention is an anthrapyridone compound characterized in that the form of the free acid is represented by the following general formula (I).

(In the formula, R ₁ represents any one selected from a hydrogen atom, an alkoxycarbonyl group, and a benzoyl group, and R ₂ represents a hydrogen atom or an alkyl group.)

  The anthrapyridone compound represented by the general formula (I) may be provided as a dicarboxylic acid derivative or a salt thereof. The anthrapyridone compound represented by the above general formula (I) can be used in preparing an ink having color developability in a blue region. When an image is formed, the color developability and image fastness (light resistance, gas resistance) It is a violet dye compound that can give an image excellent in both properties.

The water-based ink according to the present invention includes the anthrapyridone compound having the above-described form.
The ink jet recording method according to the present invention is characterized in that the above-described water-based ink is used as an ink in an ink jet recording method in which ink droplets are ejected according to a recording signal to perform recording on a recording medium. Another aspect of the ink jet recording method according to the present invention is an ink jet recording method in which ink droplets are ejected in accordance with a recording signal to perform recording on a recording medium. And a water-based ink containing a cyan pigment component together.

  The anthrapyridone compound according to the present invention is excellent in water solubility and can be used as a color material suitable for producing a blue-based aqueous ink. In addition, the ink according to the present invention and the ink-jet recorded matter recorded by the ink-jet recording method using the ink are different from the conventional ink using a blue color material, and have good image color development and image fastness. It has a feature that an image having good (light resistance and gas resistance) can be formed.

The novel anthrapyridone compound according to the present invention is characterized in that the form of the free acid is represented by the following general formula (I), and of course, a dicarboxylic acid derivative or a salt thereof is also included. The compound is particularly a water-soluble compound that can be used as a coloring material for purple to blue water-based inks.

In the general formula (I), R ₁ represents any one selected from a hydrogen atom, an alkoxycarbonyl group (ROCO—), and a benzoyl group (Ph—CO—). Specific examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 1 to 4 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, and an n-butoxycarbonyl group. it can. Such an alkoxycarbonyl group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, an amino group, and a hydroxy group. The benzoyl group (PhCO-, Ph is a benzene ring) may have a substituent, and examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a phenyl group, a halogen atom, a nitro group, an amino group, and a hydroxy group. And carboxyl groups.

In the general formula (I), examples of the substituent represented by R ₂ include a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. Such an alkyl group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, an amino group, and a hydroxy group.

As a particularly preferable example of the anthrapyridone compound according to the present invention, a dicarboxylic acid derivative of an anthrapyridone compound in which R ₁ is an unsubstituted benzoyl group and R ₂ is a methyl group in the above general formula (I) Or a salt thereof, a dicarboxylic acid derivative of an anthrapyridone compound, or a salt thereof, wherein R ₁ is an ethoxycarbonyl group and R ₂ is a methyl group.

  The salt of the dicarboxylic acid derivative of the anthrapyridone compound according to the present invention can be synthesized, for example, by the following method. First, 1-alkylamino-4-bromo-anthraquinone or 1-amino-4-bromo-anthraquinone is reacted with malonic acid dialkyl ester or benzoyl acetic acid alkyl ester to form a bromo group at the 4-position of the anthraquinone nucleus. An anthrapyridone compound (1) is obtained, and then this compound (1) is subjected to a condensation reaction with anilines such as diethyl 5-aminoisophthalate to obtain compound (2). Then, the resulting compound (2) is hydrolyzed to obtain the salt (3) of the dicarboxylic acid derivative of the anthrapyridone compound according to the present invention, in which the form of the free acid is represented by the general formula (I). This method is represented as follows in terms of the reaction path.

  The compound obtained as described above exists in a free acid form or a salt form thereof. Examples of the salt that can be employed in the present invention include alkali metal salts, alkaline earth metal salts, alkylamine salts, alkanolamine salts, and ammonium salts. Preferably, alkali metal salts such as sodium salt, potassium salt and lithium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, alkanolamine salt such as triisopropanolamine salt or ammonium Salt. This can be arbitrarily selected in the hydrolysis conditions.

  The water-based ink of the present invention is characterized by containing the aforementioned dicarboxylic acid derivative of an anthrapyridone compound or a salt thereof (hereinafter referred to as an anthrapyridone compound). Usually, the compound is mixed with water or an aqueous solvent (an organic solvent described later). In water). The pH of the ink is preferably about 6 to 11. When the water-based ink used in the ink jet recording printer is used, it is preferable that the pigment component has a small content of inorganic salt. In order to produce the anthrapyridone compound according to the present invention in a state with a small amount of inorganic substances, for example, by a normal method using a reverse osmosis membrane, or a dried product or a wet cake of the anthrapyridone compound according to the present invention with methanol and water. The mixture may be desalted by stirring in a mixed solvent, filtering and drying. In the latter case, the alcohol concentration may be 30% to 95% by mass, preferably 40% to 85% by mass, based on the entire mixed solvent. The amount of the mixed solvent used for the wet cake is not particularly limited, and is usually about 1 to 200 times, preferably about 2 to 100 times.

  The water-based ink according to the present invention is prepared using water as a medium, and the above-described anthrapyridone compound according to the present invention is preferably contained in the water-based ink in an amount of 0.1 to 20% by mass, more preferably 1. The content is about 10 to 10% by mass, more preferably about 2 to 8% by mass. The water-based ink according to the present invention may further contain a water-soluble organic solvent of 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. The lower limit of the water-soluble organic solvent may be 0% by mass, but is generally 5% by mass or more, more preferably 10% by mass or more, and most preferably about 10 to 30% by mass. In addition, the water-based ink of the present invention may contain various ink adjusting agents as described later in an amount of about 0 to 10% by mass, preferably 5% by mass or less. The balance other than the above components is water.

  Specific examples of the water-soluble organic solvent that can be used in the water-based ink according to the present invention include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butanol. Carboxylic acid amides such as alkanol, N, N-dimethylformamide or N, N-dimethylacetamide, lactams such as ε-caprolactam, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one, urea, 1, Cyclic ureas such as 3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one, ketones or ketos such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one Alcohol, tetrahydrofuran, dioxane and other ethers, ethylene glycol 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiglycol, polyethylene Polyols (triols) such as mono-, oligo- or polyalkylene glycols or thioglycols, glycerin, hexane-1,2,6-triols having 2 to 6 carbon units such as glycol and polypropylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether Examples thereof include C1-C4 alkyl ethers of polyhydric alcohols such as γ-butyrolactone and dimethyl sulfoxide. These water-soluble organic solvents may be used alone or in combination of two or more.

  Among the above, as water-soluble organic solvents having good miscibility with water and advantageous, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one, mono having a C 2-6 alkylene unit, Di- or trialkylene glycol, glycerin and the like can be mentioned, and more preferable examples include mono-, di- or triethylene glycol, dipropylene glycol, glycerin, dimethyl sulfoxide and the like, and in particular, N-methyl-2-pyrrolidone, N- The use of methylpyrrolidin-2-one, ethylene glycol, diethylene glycol, glycerin, dimethyl sulfoxide is preferred.

  Examples of the ink adjusting agent used in the present invention include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventing agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, and surfactants. Can be mentioned.

  Examples of antiseptic / antifungal agents include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol, and the like.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink in the range of 6 to 11 without adversely affecting the ink to be prepared. Examples include alkanolamines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or lithium carbonate, sodium carbonate, and potassium carbonate. Examples include alkali metal carbonates.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

  The ink according to the present invention can be obtained by adding, as a coloring material, water containing no impurities such as distilled water, the anthrapyridone compound according to the present invention described above, and, if necessary, other cyan dye components, It can be prepared by adding and mixing a basic organic solvent, an ink adjusting agent and the like. Further, the ink may be prepared by a method of adding and dissolving the anthrapyridone compound according to the present invention to a mixture of water, a water-soluble organic solvent, an ink adjusting agent, and the like. Moreover, it is also preferable to remove the impurities in the ink by performing filtration after preparing the ink as described above.

  The ink jet recording method according to the present invention is characterized by using the above-described water-based ink according to the present invention as ink when ink droplets are ejected in accordance with a recording signal to perform recording on a recording medium. To do. Preferable inkjet recording media that can be used at this time include, for example, paper and film. In particular, when it is used for a surface-treated material, specifically, a material having an ink receiving layer provided on a substrate such as paper or film, it exhibits excellent color developability and high image fastness. The ink receiving layer may be formed by impregnating or coating the base material with a cationic polymer, or by adding inorganic fine particles such as porous silica, alumina sol, and special ceramics that can absorb the pigment in the ink to polyvinyl alcohol or the like. It can be provided by coating the surface of the substrate together with a hydrophilic polymer such as polyvinylpyrrolidone. Of course, it can also be used for plain paper having no ink receiving layer.

  In the inkjet recording method according to the present invention, ink droplets are ejected in accordance with a recording signal and recorded on a recording medium. For example, a container containing the above-described blue-based aqueous ink according to the present invention is set in an inkjet printer. What is necessary is just to record by a normal method. Examples of the ink jet printer include a piezo type printer using mechanical vibration, a bubble jet (registered trademark) type printer using bubbles generated by heating, and the like.

  As a recording apparatus suitable for performing recording using the ink according to the present invention, thermal energy corresponding to the recording signal is given to the ink in the chamber of the recording head having the ink storage part in which these inks are stored, An apparatus for generating ink droplets by the energy is exemplified.

  FIG. 1 shows an example of an ink jet recording apparatus incorporating this head. In FIG. 1, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end and form a cantilever. The blade 61 is disposed at a position adjacent to the recording area by the recording head. In the example shown in FIG. 1, the blade 61 is held in a form protruding in the moving path of the recording head. Reference numeral 62 denotes a cap which is disposed at a home position adjacent to the blade 61 and moves in a direction perpendicular to the moving direction of the recording head so as to contact the ejection surface and perform capping. Further, reference numeral 63 in FIG. 1 denotes an ink absorber provided adjacent to the blade 61 and, like the blade 61, is held in a form protruding in the moving path of the recording head.

  The blade 61, the cap 62, and the absorber 63 constitute a discharge recovery portion 64, and the blade 61 and the absorber 63 remove moisture, dust, dust, and the like from the ink discharge port surface. Reference numeral 65 denotes a recording head which has discharge energy generating means and performs recording by discharging ink onto a recording medium facing the discharge port surface where the discharge ports are arranged. Reference numeral 66 denotes a recording head mounted with the recording head 65. It is a carriage for moving. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68. Accordingly, the carriage 66 can move along the guide shaft 67, and the recording area by the recording head 65 and its adjacent area can be moved.

  51 is a paper feed unit for inserting a recording medium, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording medium is fed to a position facing the ejection port surface of the recording head, and is discharged to a paper discharge unit provided with a paper discharge roller 53 as recording progresses.

  In the above configuration, when the recording head 65 returns to the home position due to the end of recording or the like, the cap 62 of the ejection recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 is in contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to protrude into the moving path of the recording head.

  When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as that at the time of wiping described above. As a result, even in this movement, the ejection port surface of the recording head 65 is wiped. The above-mentioned movement of the recording head to the home position is performed not only at the end of recording or at the time of recovery of ejection, but also to the home position adjacent to the recording area at a predetermined interval while the recording head moves the recording area for recording. In accordance with this movement, the wiping is performed.

  FIG. 2 is a cross-sectional view showing an example of an ink cartridge 45 that contains ink supplied to the head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink container, for example, an ink bag, in which supply ink is stored, and a rubber plug 42 is provided at the tip thereof. By inserting a needle (not shown) into the stopper 42, the ink in the ink bag 40 can be supplied to the head. An ink absorber 44 receives waste ink.

  The ink jet recording apparatus used in the present invention is not limited to the one in which the recording head and the ink cartridge as described above are separated, and an apparatus in which they are integrated as shown in FIG. 3 is also preferably used. . In FIG. 3, reference numeral 70 denotes a recording unit, in which an ink containing portion containing ink, for example, an ink absorber is housed, and the ink in the ink absorber has a plurality of orifices. 71 is ejected as ink droplets. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. The recording unit 70 is used in place of the recording head 65 shown in FIG. 1, and is detachable from the carriage 66.

  FIG. 4 shows an example of an ink jet cartridge that can be mounted on the above-described ink jet recording apparatus. The cartridge 1012 in this example is of a serial type, and a main part is constituted by the ink jet recording head 100 and an ink tank 1001 for containing a liquid such as ink. The ink jet recording head 100 is formed with a large number of ejection ports 832 for ejecting liquid, and the liquid such as ink is common to the ink jet recording head that ejects ink from the ink tank 1001 through an ink supply passage (not shown). It is led to the liquid chamber. A cartridge 1012 shown in FIG. 4 integrally forms an ink jet recording head 100 and an ink tank 1001 so that ink can be supplied into the ink tank 1001 as necessary. On the other hand, a structure in which the ink tank 1001 is connected in a replaceable manner may be adopted.

  Next, an Example and a comparative example are given and this invention is demonstrated concretely. The present invention is not limited by the following examples unless it exceeds the gist. In the text, “part” or “%” is based on mass unless otherwise specified.

<Example 1>
Compound A1 having the following structure was synthesized as follows.

(1) While stirring using 58.7 g of ODB (orthodichlorobenzene) as a solvent, 18.0 g (56.9 mmol) of 1-methylamino-4-bromo-anthraquinone as a raw material, 0.95 g of sodium carbonate, Benzoyl acetic acid ethyl ester (21.9 g, 113.9 mmol) was sequentially charged and the temperature was raised. And it stirred for 7 hours at the temperature of 175 degreeC, and reacted. Next, after cooling to precipitate crystals, column chromatography purification with chloroform / methanol = 100/1 was performed to obtain 17.2 g of brown crystals. This was further recrystallized from chloroform / methanol and dried to obtain 14.1 g of yellow crystals (compound 1) (see the following formula).

  The obtained yellow crystals (Compound 1) were subjected to NMR analysis, infrared spectroscopic analysis, and elemental analysis to confirm the structure. The analysis results are shown below.

[Results of Analysis for Compound 1]
[1] Results of H ¹ NMR (270 MHz, CDCl ₃ , room temperature):
δ _H (CDCl ₃ ) = 7.81 (2H), 7.67 (1H), 7.65 (1H), 7.54 (1H), 7.45 (2H), 7.40 (2H), 7 .39 (1H), 7.24 (1H), 2.78 (3H)

[2] Results of infrared spectroscopic analysis (KBr method):
ν _max / cm ⁻¹ : 1662, 1622, 1442, 1410, 1350, 1305, 1275, 1140

[3] Results of elemental analysis:
Analytical value: C = 64.58%; H = 3.08%; N = 3.05%
(Theoretical value when C ₂₄ H ₁₄ NO ₃ Br is used: C = 64.88%; H = 3.18%; N = 3.15%)

(2) Next, while stirring 30.0 g of DMI (1,3-dimethyl-2-imidazolidinone) as a solvent, 12.0 g (27.0 mmol) of the compound 1 obtained above was mixed with 5- 9.6 g (40.5 mmol) of diethyl aminoisophthalate, 4.3 g of sodium carbonate, and 3.4 g of copper powder were sequentially charged and heated. And it stirred for 3.5 hours at the temperature of 192 degreeC, and reacted. Then, after cooling and diluting with ethyl acetate, filtration was performed to remove unreacted sodium carbonate and copper powder. Further, the solvent was removed from the filtrate with an evaporator, and silica gel column chromatography purification (toluene / THF = 50/1 → 20/1) was performed to obtain 14.1 g of dark purple crystals (compound 2) (see the following formula) ).

  The obtained deep purple crystal (Compound 2) was subjected to NMR analysis, infrared spectroscopic analysis, and elemental analysis to confirm the structure. The analysis results are shown below.

[Analysis results for Compound 2]
[1] Results of H ¹ NMR (270 MHz, CDCl ₃ , room temperature):
δ _H (CDCl ₃ ): 8.04 (1H), 7.81 (2H), 7.65 (1H), 7.54 (1H), 7.53 (1H), 7.45 (2H), 7 .40 (2H), 7.38 (2H), 7.24 (1H), 6.42 (1H), 4.29 (4H), 2.78 (3H), 1.30 (6H)

[2] Results of infrared spectroscopic analysis (KBr method):
ν _max / cm ⁻¹ : 3450, 1725, 1675, 1620, 1551, 1315, 1282, 1242

[3] Results of elemental analysis:
Analytical value: C = 71.89%; H = 4.81%; N = 4.63%
(Theoretical value in the case of C ₃₆ H ₂₈ N ₂ O ₇ : C = 71.9%; H = 4.70%; N = 4.66%)

(3) Then, 20 g of THF (tetrahydrofuran) and 10 ml of methanol were used as solvents in a water bath, and 1.3 g (2.16 mmol) of the compound 2 obtained above was dissolved. Then, 10 ml of a 10% sodium hydroxide aqueous solution is dropped at a temperature of 11 ° C. to 23 ° C., and after completion of the dropping, the temperature is raised to 35 ° C. and stirred for 3 hours. After completion of the reaction, the reaction mixture was diluted with THF, filtered, and the crystal was washed with THF to obtain 1.0 g of the target purple crystal A1 (compound 3, R ₁ : benzoyl group, R ₂ : methyl group) (the following formula: reference).

  About the obtained purple crystal (compound 3), NMR analysis, infrared spectroscopic analysis, and elemental analysis were performed to confirm the structure. The analysis results are shown below.

[Analysis results for Compound 3]
[1] Results of H ¹ NMR (270 MHz, D ₂ O, room temperature):
δ _H (D ₂ O): 8.36 (1H), 7.81 (2H), 7.67 (2H), 7.65 (1H), 7.54 (1H), 7.53 (1H), 7.45 (2H), 7.40 (2H), 7.24 (1H), 6.42 (1H), 2.78 (3H)

[2] Results of infrared spectroscopic analysis (KBr method):
ν _max / cm ⁻¹ : 3400, 1615, 1565, 1441, 1371, 1285, 1184, 992

[3] Results of elemental analysis:
Analytical value: C = 65.21%; H = 3.18%; N = 4.79%
(Theoretical value when C ₃₂ H ₁₈ N ₂ O ₇ Na ₂ is used: C = 65.31%; H = 3.08%; N = 4.76%)

<Example 2>
Compound A2 having the following structure was synthesized as follows.

(1) 18.0 g (56.9 mmol) of 1-methylamino-4-bromo-anthraquinone, 0.95 g of sodium carbonate, and 18.2 g of diethyl malonate as raw materials while stirring using 58.7 g of ODB as a solvent 113.9 mmol) was sequentially charged and the temperature was raised. And it stirred for 6 hours at the temperature of 176 degreeC, and reacted. Next, after cooling to precipitate crystals, column chromatography purification (chloroform / methanol = 100/1) was performed to obtain 14.4 g of brown crystals. This was further recrystallized from chloroform / methanol and dried to obtain 11.7 g of yellow crystals (compound 4) (see the following formula).

  The obtained yellow crystals (compound 4) were subjected to NMR analysis, infrared spectroscopic analysis, and elemental analysis to confirm the structure. The analysis results are shown below.

[Analysis results for Compound 4]
[1] Results of H ¹ NMR (270 MHz, CDCl ₃ , room temperature):
δ _H (CDCl ₃ ): 7.67 (1H), 7.65 (1H), 7.40 (2H), 7.39 (1H), 7.24 (1H), 4.19 (2H), 2 .78 (3H), 1.30 (3H)

[2] Results of infrared spectroscopic analysis (KBr method):
ν _max / cm ⁻¹ : 1722, 1631, 1411, 1361, 1305, 1275, 1125, 1025

[3] Results of elemental analysis:
Analytical value: C = 58.27%; H = 3.42%; N = 3.40%
(Theoretical value when C ₂₀ H ₁₄ NO ₄ Br is used: C = 58.27%; H = 3.42%; N = 3.40%)

(2) Next, 9.0 g (21.8 mmol) of the compound 4 obtained above, 7.8 g (32.7 mmol) of diethyl 5-aminoisophthalate, sodium carbonate with stirring while using 20.0 g of DMI as a solvent 3.5 g (32.7 mmol) and 2.8 g (43.6 mmol) of copper powder were sequentially charged and the temperature was raised. And it stirred at the temperature of 173 degreeC for 3 hours, and reacted. Then, after cooling and stopping the reaction with water, it was filtered to remove unreacted sodium carbonate and copper powder. Further, the solvent was removed from the filtrate with an evaporator, and silica gel column chromatography purification (toluene / THF = 20/1 → 10/1) was performed to obtain 2.4 g of reddish brown crystals (compound 5) (see the following formula). .

  The obtained reddish brown crystals (Compound 5) were subjected to NMR analysis, infrared spectroscopic analysis, and elemental analysis to confirm the structure. The analysis results are shown below.

[Analysis results for Compound 5]
[1] Results of H ¹ NMR (270 MHz, CDCl ₃ , room temperature):
δ _H (CDCl ₃ ): 8.04 (1H), 7.65 (1H), 7.53 (1H), 7.40 (2H), 7.38 (2H), 7.24 (1H), 6 .42 (1H), 4.29 (4H), 4.19 (2H), 2.78 (3H), 1.30 (9H)

[2] Results of infrared spectroscopic analysis (KBr method):
ν _max / cm ⁻¹ : 3425, 2975, 1715, 1615, 1506, 1450, 1365, 1305, 1235, 1030

[3] Results of elemental analysis:
Analytical value: C = 67.50%; H = 4.95%; N = 4.91%
(Theoretical value when C ₃₂ H ₂₈ N ₂ O ₈ is used: C = 67.60%; H = 4.96%; N = 4.93%)

(3) Next, 2.3 g (4.04 mmol) of the compound 5 obtained above is dissolved in a water bath using 20 ml of THF and 5 ml of methanol as a solvent. At room temperature, 3.5 ml of a 10% aqueous sodium hydroxide solution was added dropwise, and after completion of the addition, the reaction was allowed to stir for 7 hours. After completion of the reaction, it was diluted with THF, filtered, and the crystal was washed with THF to obtain 1.9 g of the intended purple crystal A2 (compound 6, R ₁ : ethoxycarbonyl group, R ₂ : methyl group) (the following formula See).

  The obtained purple crystal (Compound 6) was subjected to NMR analysis, infrared spectroscopic analysis, and elemental analysis to confirm the structure. The analysis results are shown below.

[Analysis results for Compound 6]
[1] Results of H ¹ NMR (270 MHz, D ₂ O, room temperature):
δ _H (D ₂ O): 8.36 (1H), 7.67 (2H), 7.65 (1H), 7.53 (1H), 7.40 (2H), 7.24 (1H), 6.42 (1H), 4.19 (2H), 2.78 (3H), 1.30 (3H)

[2] Results of infrared spectroscopic analysis (KBr method):
ν _max / cm ⁻¹ : 3400, 1731, 1620, 1571, 1451, 1372, 1285, 1184

[3] Results of elemental analysis:
Analytical value: C = 66.42%; H = 3.25%; N = 5.01%
(Theoretical value when C ₂₈ H ₁₈ N ₂ O ₈ Na ₂ is used: C = 60.44%; H = 3.26%; N = 5.03%)

<Example 3>
(Preparation of recording ink 1)
The following components containing A1 obtained above were mixed, and further filtered under pressure with a membrane filter having a pore size of 0.2 microns to obtain recording ink 1.
・ Compound A1 4 parts ・ Diethylene glycol 5 parts ・ Glycerin 10 parts ・ Acetylenol EH (manufactured by Kawaken Fine Chemicals)
1 part, 80 parts of ion exchange water

<Example 4>
(Preparation of recording ink 2)
The following components containing A1 obtained above were mixed, and further filtered under pressure with a membrane filter having a pore size of 0.2 microns to obtain recording ink 2.
Compound A1 4 parts C.I. I. Direct Blue 199 1 part ・ Diethylene glycol 5 parts ・ Glycerin 10 parts ・ Acetylenol EH (manufactured by Kawaken Fine Chemicals)
1 part, 79 parts of ion exchange water

<Example 5>
(Preparation of recording ink 3)
The following components containing A2 obtained above were mixed, and further filtered under pressure with a membrane filter having a pore size of 0.2 microns to obtain recording ink 3.
・ Compound A2 4 parts ・ Diethylene glycol 5 parts ・ Glycerin 10 parts ・ Acetyleneol EH (manufactured by Kawaken Fine Chemicals)
1 part, 80 parts of ion exchange water

<Example 6>
(Preparation of recording ink 4)
The following components containing A2 obtained above were mixed, and further filtered under pressure with a membrane filter having a pore size of 0.2 microns to obtain recording ink 4.
Compound A2 3 parts C.I. I. Direct Blue 199 1 part ・ Diethylene glycol 5 parts ・ Glycerin 10 parts ・ Acetylenol EH (manufactured by Kawaken Fine Chemicals)
1 part, 80 parts of ion exchange water

<< Evaluation >>
The recording inks 1 to 4 of the examples prepared as described above were packed in an ink cartridge for BJF-900 (manufactured by Canon Inc.), and resolution of 1200 × 1200 dpi using BJF-900 (manufactured by Canon Inc.). Thus, a solid image was formed with a discharge amount of 4.5 pl per nozzle. About each obtained image, color development property, light resistance, and gas resistance were evaluated by the following method and reference | standard. The recording medium used for printing was a gloss media PR-101 for inkjet manufactured by Canon Inc. Table 1 shows the obtained evaluation results.

The evaluation method is described below. In each test, after printing, the obtained image was evaluated after being left for 12 hours or more at room temperature and normal humidity.
(1) Color development evaluation apparatus: Ci35 manufactured by Macbeth
Evaluation method: L ^* , a ^* , and b ^* of the test sample were measured, and C ^* and h were calculated by the following equations.
C ^* = (a ^{* 2} + b ^{* 2} ) ^1/2
h = tan ⁻¹ (b ^* / a ^* )

(2) Light resistance Device: Atlas fade meter manufactured by Atlas Co., Ltd. Exposure condition: 30 hours with xenon lamp 0.39 W / m ² Evaluation device: Same as used for color development evaluation Evaluation method: Color difference in CIELab space before and after the test ( ΔE) was measured.

(3) Gas resistance Using a self-made ozone generator, ozone was exposed to printed matter under the following conditions.
Exposure condition: 2 hours at an ozone concentration of 3 ppm Evaluation device: The same device used for color development evaluation Evaluation method: Color difference (ΔE) in CIELab space before and after the test was measured.

  The anthrapyridone compound of the present invention is excellent in water solubility and can be used as a coloring material for purple or blue water-based inks. The obtained violet or blue ink and the ink-jet recorded matter recorded by the ink-jet recording method using the ink are different from the inks using the blue dyes so far and have good color development and image fastness. Characteristics (light resistance, gas resistance) are also good.

It is a perspective view which shows an example of an inkjet recording device. It is a longitudinal cross-sectional view of an ink cartridge. It is a perspective view of a recording unit. It is a schematic perspective view which shows an example of the inkjet cartridge provided with the inkjet recording head.

Explanation of symbols

40: Ink bag 42: Plug 44: Ink absorber 45: Ink cartridge 51: Paper feed unit 52: Paper feed roller 53: Paper discharge roller 61: Blade 62: Cap 63: Ink absorber 64: Ejection recovery unit 65: Recording Head 66: Carriage 67: Guide shaft 68: Motor 69: Belt 70: Recording unit 71: Head unit 72: Atmospheric communication port 100: Inkjet recording head 832: Ejection port 1001: Ink tank 1012: Cartridge

Claims (8)

An anthrapyridone compound characterized in that the form of the free acid is represented by the following general formula (I).

(In the formula, R ₁ represents any one selected from a hydrogen atom, an alkoxycarbonyl group, and a benzoyl group, and R ₂ represents a hydrogen atom or an alkyl group.) The anthrapyridone compound according to claim 1, wherein R ₁ in the general formula (I) is an unsubstituted benzoyl group, and R ₂ is a methyl group. The anthrapyridone compound according to claim 1, wherein R ₁ in the general formula (I) is an ethoxycarbonyl group and R ₂ is a methyl group.   An aqueous ink comprising the anthrapyridone compound according to any one of claims 1 to 3 as a pigment component.   The water-based ink according to claim 4, further comprising water and a water-soluble organic solvent.   The water-based ink according to claim 4 or 5, which is for inkjet recording.   7. An ink jet recording method for recording on a recording medium by ejecting ink droplets according to a recording signal, wherein the water-based ink according to claim 4 is used as the ink. Method. 4. In an inkjet recording method for recording on a recording medium by ejecting ink droplets according to a recording signal, at least one anthrapyridone compound according to claim 1 and a cyan dye as a blue component An ink jet recording method comprising using a water-based ink containing both components.

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