JP2006188706A - New anthrapyridone compound, aqueous magenta ink composition and ink jet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clear magenta compound suitable for ink-jet recording exhibiting lightfast and water-resistant recorded documents. <P>SOLUTION: An aqueous ink composition comprises anthrapyridone compounds shown by a formula A-B [in which A represents a pigment residue of formula (1) wherein R<SB>1</SB>represents a hydrogen atom, an alkoxycarbonyl or benzoyl group, R<SB>2</SB>represents a hydrogen atom or a methyl group, and B represents a hydrogen atom or a substituent] or their salts, and an ink-jet printing method using the aqueous ink composition is provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel anthrapyridone compound, an aqueous magenta ink composition, and an ink jet recording method.

  Various ink ejection methods have been developed as recording methods using an ink jet printer, but all of them generate ink droplets and attach them to various recording materials (paper, film, fabric, etc.) for recording. Is. The recording method using an ink jet printer has been rapidly spread in recent years due to the fact that the recording head and the recording material do not contact each other and no noise is generated and the printer is quiet, and the printer is smaller, faster, and easier to color. Large growth is expected in the future. In order to record an image or character information on a color display of a computer with an ink jet printer in color, generally, four color inks of yellow (Y), magenta (M), cyan (C), and black (K) are used. Expressed in subtractive color mixing. In order to faithfully reproduce additive color-mixed images using R, G, B such as CRT displays with subtractive color-mixed images, the dyes used, especially the dyes used for YMC ink, have hues that are as close to YMC standards as possible. However, it is desired to be clear. Further, the ink composition is required to be stable for long-term storage, to have a high density of printed images, and to be excellent in fastness such as water resistance and light resistance. The present invention relates to magenta ink.

  The anthrapyridone compound of the present invention is excellent in water solubility, and has a feature of good filterability in filtration with a membrane filter that is carried out as necessary in the process of producing an ink composition. Moreover, this pigment | dye has high safety | security with respect to a biological body. The ink composition of the present invention using this novel anthrapyridone compound is free of crystal precipitation, physical property change, color change and the like after long-term storage, not only in winter but also in summer, and has good storage stability. In addition, the printed matter using the ink composition of the present invention as a magenta ink for ink jet recording is excellent in light resistance and water resistance, and can be used in combination with yellow, cyan and black dyes to enable ink jet recording excellent in light resistance and water resistance. It is. Further, excellent light resistance can be maintained even when used in combination with a metal-containing phthalocyanine dye as cyan. Furthermore, the printing surface is clear and has a magenta color that is close to ideal as a color characteristic. By using it with other yellow and sheer inks, it is possible to produce a color tone in a wide visible region. Therefore, the ink composition of the present invention is extremely useful as a magenta ink for inkjet recording.

Applications of inkjet printers are expanding from OA small printers to industrial large printers, and robustness such as water resistance and light resistance is required more than ever. Water resistance is greatly improved by coating the surface of paper with inorganic fine particles capable of adsorbing pigments in ink such as porous silica together with PVA resin and the like, and various coated papers for inkjet printing are already on the market. However, a technology for greatly improving light resistance has not been established. In particular, among the four primary colors Y, M, C, and K, many of magenta dyes originally have low light resistance, and the improvement is an important issue. It has become.

Representative examples of magenta dye skeletons used in water-soluble inks for inkjet recording include xanthene compounds found in Patent Documents 1-3 and the like, and H acid azo compounds found in Patent Documents 4-8 and the like. Among these, the xanthene type has very good hue and sharpness but very poor light resistance. Some H acid azo compounds have good hue and water resistance, but are inferior in light resistance and sharpness. As seen in Patent Document 6, a magenta dye excellent in sharpness and light resistance has also been developed, but still has light resistance compared to other hue dyes such as cyan and yellow dyes typified by copper phthalocyanine. Inferior level.

Further, magenta dye skeletons with excellent sharpness and light resistance include anthrapyridone systems as found in Patent Documents 9 and 10, etc., which satisfy all of hue, sharpness, light resistance, water resistance and dissolution stability. Is not obtained.
An object of the present invention is to provide a magenta water-based ink composition having a hue and clearness suitable for ink jet recording and having strong light fastness and water fastness of recorded matter.
JP 54-89811 A JP-A-8-60053 JP-A-8-143798 JP 61-62562 A JP-A-62-156168 JP-A-3-203970 JP-A-7-157698 No. 7-78190 JP 59-74173 Japanese Patent Laid-Open No. 2-16171

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
(1) Formula AB
(In the formula, A represents the following formula (1)

(Wherein R ₁ represents a hydrogen atom, an alkoxycarbonyl group or a benzoyl group, and R ₂ represents a hydrogen atom or a methyl group.)
And B represents a hydrogen atom or a substituent on the dye residue A. )
An anthrapyridone compound represented by
(2) B is an acyl group or the following formula (2)

(Wherein X and Y are each independently a chlorine atom, hydroxyl group, amino group, monoethanolamino group, diethanolamino group, morpholino group, or anilino group (from sulfonic acid group, carboxyl group, methyl group, chlorine atom) Which may be substituted with one or more selected substituents)).
In formula (2) of the anthrapyridone compound or a salt thereof (3) or (2) according to (1), wherein X is an anilino group (one selected from a sulfonic acid group and a carboxyl group, or 2 An anthrapyridone compound or a salt thereof according to (2), which may be substituted with a substituent of a species, and Y is a chlorine atom, a hydroxyl group, an amino group, a monoethanol group, a diethylol group or a morpholino group,
(4) The anthrapyridone compound or a salt thereof according to (2), wherein the acyl group is a benzenesulfonyl group, a tosyl group, a 2-carboxy-benzoyl group, or a 3,4-dicarboxybenzoyl group,
(5) An anthrapyridone compound or a salt thereof according to claim 1, wherein R ₁ is a hydrogen atom, and R ₂ is a methyl group.
(6) A water-based magenta ink composition comprising the anthrapyridone compound or a salt thereof according to (1) to (5) as a dye component,
(7) The aqueous magenta ink composition as described in (6) containing water and an organic solvent (8) The content in the anthrapyridone compound or a salt thereof is 1% by weight or less, as described in (6) or (7) Aqueous magenta ink composition,
(9) The aqueous magenta ink composition according to any one of (6) to (8), which is for inkjet recording.
(10) In an ink jet recording method for recording on a recording material by ejecting ink droplets according to a recording signal, the water-based magenta ink composition according to any one of (6) to (8) is used as ink. An ink jet recording method comprising:
(11) In the ink jet recording method for recording on a recording material by ejecting ink droplets according to a recording signal, the aqueous magenta ink composition according to any one of (6) to (8) is used as a magenta ink. An ink jet recording method characterized by using a water-based ink containing a water-soluble metal phthalocyanine dye as a cyan ink,
(12) The inkjet recording method according to (11), wherein the recording material is an information transmission sheet,
(13) The inkjet recording method according to (12), wherein the information transmission sheet is a surface-treated sheet,
(14) An inkjet printer having a container containing the aqueous magenta ink composition according to any one of (6) to 8 and a container containing an aqueous cyan ink composition containing a water-soluble metal phthalocyanine dye,
(15) The anthrapyridone compound or a salt thereof according to (1), wherein R ₁ is a hydrogen atom or a lower alkoxycarbonyl group, R ₂ is a methyl group, B is a hydrogen atom or a C _{1 to} C ₄ alkoxycarbonyl group.

  The novel anthrapyridone compound of the present invention is represented by the formula AB. The dye residue A is a dye residue represented by the formula (1), and B is a hydrogen atom or a substituent on the dye residue A. That is, the present invention is an anthrapyridone compound having a group represented by the formula (1) as a pigment residue. This anthrapyridone compound preferably has a group represented by the formula (1) as a pigment residue and is a water-soluble compound used as a magenta (blue-red) pigment component.

In the formula (1), examples of the alkoxycarbonyl group of R ₁ include C ₁ -C ₄ alkoxy such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group and the like. An example is a carbonyl group. Further, the substituent on the dye residue A represented by B is not particularly limited as long as it is a group that can be substituted with a nitrogen atom. For example, an acyl group or a group represented by the above formula (2), a substituent can be substituted. Examples thereof include an optionally substituted C _{1 to} C ₄ alkyl group. Preferred examples of the dye residue A include those in which R ₁ is a hydrogen atom and R ₂ is a methyl group in the general formula (1).
Examples of the acyl group include a substituted or unsubstituted benzenesulfonyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted benzoyl group, and a substituted or unsubstituted alkoxycarbonyl group. Alkyl C ₁ -C ₄ The substituent on the benzene nucleus in these groups, a phenyl group, a halogen atom, a nitro group, an amino group, hydroxy group, can be exemplified carboxyl group, these substituents Among them, those that may further have a substituent may be substituted with the above-described substituent. Examples of the substituent of the alkyl group include those listed as substituents that can be substituted on the benzene nucleus (excluding the alkyl group). Specific examples of these acyl groups include, for example, lower alkyl-substituted benzenesulfonyl groups such as benzenesulfonyl group and tosyl group, halogenobenzenesulfonyl groups such as 4-chlorobenzenesulfonyl group and 4-bromobenzenesulfonyl group, methylsulfonyl group, C ₁ -C ₄ alkylsulfonyl group such as ethylsulfonyl group, benzoyl group, 3,4-dicarboxybenzoyl group or other optionally substituted benzoyl group, phenylacetyl group, acetyl group or the like may be substituted Preferred examples thereof include an optionally substituted alkoxycarbonyl group such as a lower alkylcarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group and a benzyloxycarbonyl group.

In the formula (2), examples of the anilino group which may be substituted with one or two or more substituents selected from a sulfonic acid group, a carboxyl group, a methyl group and a chlorine atom include 2,5-disulfoanilino, for example. Group, 3-sulfoanilino group, 2-sulfoanilino group, 4-sulfoanilino group, 2-carboxy-4-sulfoanilino group, 2-carboxy-5-sulfoanilino group and the like.
X in the formula (2) is preferably an anilino group which may be substituted with a substituent, more preferably an anilino group having at least one sulfonic acid group.

In the anthrapyridone compound represented by the formula AB of the present invention, R ₁ in the formula (1) is a hydrogen atom or a lower alkoxycarbonyl group, more preferably a hydrogen atom, and R ₂ is a methyl group. , B represents the formula (2), X in the formula (2) is an anilino group having at least one sulfonyl group, and Y is a hydroxy group or an amino group.
In the anthrapyridone compound, R ₁ is a hydrogen atom or an alkoxycarbonyl group, R ₂ is a methyl group, B is a hydrogen atom or a C _{1 to} C ₄ alkoxycarbonyl group, or a salt thereof. It is also important as an intermediate for synthesizing compounds.
Specific examples of the anthrapyridone compound represented by Formula AB of the present invention are shown in Table 1. In Table 1, (S) is a sulfonic acid group, 2 (S) is a disulfonic acid group, (K) is a carboxy group, 2 (K) is a dicarboxy group, E is an ethoxycarbonyl group, M Represents a methoxycarbonyl group, Ph represents a phenyl group, and Bz represents a benzoyl group.

Table 1
No. A B
Formula (1) Formula (2)
R ₁ R ₂ X Y
1 H CH3 COCH3
2 H CH3 H
3 H CH3 2,5-2 (S) -anilino Cl
4 H CH3 2,5-2 (S) -anilino OH
5 H CH3 2,5-2 (S) -anilino NH2
6 H CH3 2,5-2 (S) -anilino morpholino 7 H CH3 2,5-2 (S) -anilino di (hydroxyethyl)
Amino 8 H CH3 2,5-2 (S) -anilino Hydroxyethylamino 9 H CH3 3- (S) -anilino Cl
10 H CH3 3- (S) -anilino OH
11 H CH3 2- (S) -anilino Cl
12 H CH3 2- (S) -anilino OH

13 H CH3 4- (S) -anilino Cl
14 H CH3 4- (S) -anilino OH
15 H CH3 2- (K) -4- (S) -anilino Cl
16 H CH3 2- (K) -4- (S) -anilino OH
17 H CH3 2- (K) -4- (S) -anilino NH2
18 H CH3 2- (K) -5- (S) -anilino Cl
19 H CH3 2- (K) -5- (S) -anilino OH
20 H CH3 2- (K) -5- (S) -anilino NH2
21 E CH3 2,5-2 (S) -anilino Cl
22 E CH3 2,5-2 (S) -anilino OH
23 MH 2,5-2 (S) -anilino Cl
24 MH 2,5-2 (S) -anilino OH
25 H CH3 2,5-2 (S) -anilino 2,5-2 (S) -anilino

26 H CH3 2,5-2 (S) -anilino 2- (S) -anilino
27 H CH3 Tosyl
28 H CH3 Benzenesulfonyl
29 H CH3 Benzoyl
30 H CH3 3,4-2 (K) -benzoyl
31 H CH3 Methylzensulfonyl
32 H CH3 4-Cl-benzenesulfonyl
33 H CH3 Ph-acetyl
34 H CH3 ethoxycarbonyl
35 H CH3 benzyloxycarbonyl
36 E CH3 Tosyl
37 E CH3 Benzenesulfonyl

38 E CH3 Benzoyl
39 E CH3 3,4-2 (K) -benzoyl
40 E CH3 Methylzensulfonyl
41 E CH3 4-Cl-benzenesulfonyl
42 E CH3 Ph-acetyl
43 E CH3 Ethoxycarbonyl
44 E CH3 Benzyloxycarbonyl
45 E CH3 COCH3
46 E CH3 H
47 Bz CH3 2,5-2 (S) -anilino OH
48 E CH3 2 (K) -benzoyl

  The anthrapyridone compound of the present invention is produced, for example, by the following method. That is, the following formula (3)

(In the formula, R ₁ and R ₂ are the same as above.)
5-acetylamino-2-sulfoaniline was condensed with the bromide of anthrapyridone represented by the Ullmann reaction. 1 compound is obtained. Next, by removing the acetyl group by hydrolysis, No. 1 in which B is a hydrogen atom is obtained. 2 compounds are obtained.
When B is a group represented by the formula (2) and X in the formula (2) is a group other than a chlorine atom or a hydroxyl group, amines such as anilines corresponding to the target compound and 2, 4, 6-trichloro-s-triazine (cyanuric chloride) is condensed to give the corresponding primary condensate. By subjecting compound 2 to secondary condensation, a compound in which X is an amino group corresponding to the amines and Y is a chlorine atom is obtained. Subsequently, a compound in which Y is a hydroxyl group can be obtained by hydrolysis. When Y is a group other than a chlorine atom or a hydroxyl group, the target compound can be obtained by subjecting the compound in which Y is a chlorine atom to tertiary condensation with an amine corresponding to the target compound. When B is a group other than the substituent represented by the formula (2), The acylating agent may be reacted with the compound of 2.
Examples of the acylating agent include acyl chlorides corresponding to the acyl group. For example, a substituted or unsubstituted benzenesulfonyl chloride, a substituted or unsubstituted alkylsulfonyl chloride, a substituted or unsubstituted benzoyl chloride, a substituted or unsubstituted alkoxycarbonyl chloride, etc. can be mentioned, and specifically, benzenesulfonyl chloride. , Toluenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride, methylsulfonyl chloride, ethylsulfonyl chloride, benzoyljurolide, 3,4-dicarboxybenzoyl chloride, phenylacetic acid chloride, acetic acid chloride, methoxycarbonyl chloride , Ethoxycarbonyl chloride, propoxycarbonyl chloride, butoxycarbonyl chloride, benzyloxycarbonyl chloride Ride, and the like.

  The compound thus obtained exists in the form of the free acid or in the form of its salt. Examples of the salt that can be used 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.

The aqueous magenta ink composition of the present invention is obtained by dissolving the compound represented by the formula AB or a salt thereof in water or an aqueous solvent (water containing an organic solvent described later). The pH of the ink is preferably about 6-11. When this water-based ink composition is used in an ink jet recording printer, it is preferable to use a pigment component having a low content of inorganic salts such as metal cation chlorides and sulfates. For example, the total content of sodium chloride and sodium sulfate is 1% by weight or less.
In order to produce the pigment component of the present invention (compound represented by the formula AB) or a salt thereof having a small amount of inorganic substances, for example, a conventional method using a reverse osmosis membrane or a dried product or wet cake of the anthrapyridone compound of the present invention May be desalted by stirring in a mixed solvent of methanol and water, filtering, and drying. In the latter case, the alcohol concentration is 30% to 95% by weight, preferably 40% to 85% by weight, based on the entire mixed solvent. The amount of the mixed solvent used for the wet cake is not particularly limited, and is usually 1 to 200 times, preferably about 2 to 100 times.
The contents of NaCl and Na ₂ SO _{4 in} the inorganic salt are converted after measuring the amount of Cl ions or SO ₄ ions with an ion chromatograph. Heavy metals are measured by atomic absorption or ICP (Industrial Coupled Plasma) emission analysis, and calcium ions and magnesium are measured by ion chromatography, atomic absorption, and ICP emission analysis.

  The water-based ink composition of the present invention is prepared using water as a medium. The anthrapyridone compound of the present invention or a salt thereof is preferably 0.1 to 20% by weight in the water-based ink composition, more preferably 1 to The content is about 10% by weight, more preferably about 2 to 8% by weight. The water-based ink composition of the present invention further contains a water-soluble organic solvent of about 60% by weight or less, preferably about 50% by weight or less, more preferably about 40% by weight or less, and further preferably about 30% by weight or less. The lower limit may be 0% by weight, but is generally about 5% by weight or more, more preferably 10% or more, and most preferably about 10 to 30% by weight. The aqueous ink composition of the present invention may contain an ink preparation agent in an amount of about 0 to 10% by weight, preferably 5% by weight or less. The balance other than the above components is water.

Specific examples of the water-soluble organic solvent which can be used include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, C ₁ -C ₄ alkanol such as tert-butanol, N, N-dimethylformamide or Carboxylic acid amides such as N, N-dimethylacetamide, ε-caprolactam, lactams such as N-methylpyrrolidin-2-one, urea, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydro Cyclic ureas such as pyrimido-2-one, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or ethers such as ketoalcohol, tetrahydrofuran, dioxane, ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-also 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, mono having C ₂ -C ₆ alkylene units, such as polypropylene glycol, oligo- or Polyalkylene glycol or thioglycol, glycerin, polyol (triol) such as hexane-1,2,6-triol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ethers, C ₁ -C ₄ alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl ether, gamma Buchirorakuto Or dimethyl sulfoxide, and the like. Two or more of these organic solvents may be used in combination.

Advantageous organic solvents miscible good with water, N- methyl-2-pyrrolidone, N- methylpyrrolidin-2-one, mono- having C ₂ -C ₆ alkylene units, di- or tri-alkylene glycol. More preferable examples include mono-, di- or triethylene glycol, dipropylene glycol, dimethyl sulfoxide and the like, and in particular, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one, ethylene glycol, The use of diethylene glycol, glycerin, dimethyl sulfoxide, N-methyl-2-pyrrolidone is preferred.

  Examples of the ink preparation agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye dissolving agents, and surfactants. Examples of antiseptic / antifungal agents include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, 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 thereof 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 inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  The ink composition of the present invention is prepared by adding and mixing the dye and, if necessary, the water-soluble organic solvent, the ink preparation agent, and the like into water that does not contain impurities such as distilled water. The dye may be added to and dissolved in a mixture of water and the water-soluble organic solvent, ink preparation agent or the like. Further, after the ink composition is obtained, filtration may be performed to remove impurities.

  In the ink jet recording method of the present invention, examples of a preferable recording material that can be used include an information transmission sheet such as paper and film. The information transmission sheet is a printing sheet that does not require any special pre-processing prior to printing and does not require post-processing even after printing by an ink jet printer. As the information transmission sheet, a surface-treated sheet, specifically, a sheet in which an ink receiving layer is provided on these substrates is preferable. For example, the ink receiving layer may be formed by impregnating or coating the base material with a cationic polymer, and inorganic fine particles capable of absorbing the pigment in the ink such as porous silica, alumina sol, and special ceramics. It is provided by coating the surface of the substrate together with the hydrophilic polymer. Those provided with such an ink receiving layer are usually called ink jet paper (film), glossy paper (film), etc., for example, Pictrico (manufactured by Asahi Glass Co., Ltd.), color BJ paper, color BJ photo film. Sheets (all manufactured by Canon Inc.), color image jet paper (manufactured by Sharp Corporation), Glossy Film for Super Fine (manufactured by Epson Corporation), Picta Fine (manufactured by Hitachi Maxell Corporation), etc. It is commercially available. Of course, it can also be used for plain paper.

In order to record on a recording material by the ink jet recording method of the present invention, for example, a container containing the above-mentioned aqueous magenta ink composition may be set in an ink jet printer and recorded on the recording material by a normal method. Examples of the inkjet printer include a piezo printer using mechanical vibration and a bubble jet (registered trademark) printer using bubbles generated by heating. In the inkjet recording method of the present invention, the aqueous magenta ink composition is usually used in combination with a yellow ink composition, a cyan ink composition, and, if necessary, a black ink composition. When a water-based cyan ink composition containing a water-soluble metal phthalocyanine dye is used as the cyan ink composition, by using it together with the above-mentioned water-based magenta ink composition, the color tone in the light resistance test after the color mixture of the two is obtained. This is preferable because the change can be reduced. Examples of the metal used in the water-soluble metal phthalocyanine dye include copper, nickel, and aluminum, and copper is preferable. Examples of the water-soluble copper phthalocyanine dye include C.I. 1. Direct Blue 86, C.I. I. Direct Blue 87, C.I. I. Direct Bull-199, C.I. I. Acid Blue 249, C.I. I. Reactive Blue 7, C.I. I. Reactive Blue 15, C.I. I. Reactive Blue 21, C.I. I. Reactive Bull-71 and the like.
An aqueous cyan ink composition containing a water-soluble metal phthalocyanine dye is produced, for example, according to the above-described method for producing an aqueous magenta ink composition and injected into a container, and the container contains the aqueous magenta ink composition described above. Similar to the container, it is used by being set at a predetermined position of the ink jet printer.
The water-based ink composition of the present invention is vivid and approximates the color tone designated by Japan Co., Ltd., published by the Japan Printing Industrial Machinery Manufacturers Association, and has a high saturation and a moderately bluish magenta color. By using together with other yellow and cyan inks, it is possible to develop a color tone in a wide visible region, and by selecting existing yellow, cyan, and black that have excellent light resistance and water resistance. In addition, a recorded matter having excellent light resistance and water resistance can be obtained.

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

Example 1
(1) 51.0 parts of the compound of formula (3) (R ₁ = H, R ₂ = CH ₃ ), 23.9 parts of sodium carbonate, and second acetic acid in 450 parts of N, N-dimethylformamide with stirring. 18.0 parts of copper monohydrate and 114.0 parts of 5-acetylamino-2-sulfoaniline are sequentially charged, and the temperature is raised. The reaction is performed at a temperature of 130 to 135 ° C. for 3 hours. Subsequently, the mixture was cooled, stirred at 20 ° C. for 30 minutes, filtered, washed with 300 parts of methanol, dried, 62.9 parts of compound 1 are obtained as red crystals.

  Next, 513 parts of 96% sulfuric acid was dropped into 471 parts of water under cooling to prepare 50% sulfuric acid. 61.3 parts of 1 compound are added. Heat up and react under reflux (123 ° C.) for 3 hours. Under water cooling (about 25 ° C.), the mixture is stirred for 1 hour, filtered, and washed with 120 parts of water to obtain a red wet cake. The wet cake is gradually added with stirring to a mixed solution of 2000 parts of water and 80 parts of 24% sodium hydroxide. After stirring at room temperature for 1 hour, a small amount of insoluble matter is filtered off by filtration. Under stirring, 100 parts of sodium chloride is added to the mother liquor. After stirring at room temperature for 1 hour, it was filtered and dried. 20.2 parts of compound 2 are obtained as red crystals.

  (2) Add 0.25 parts of Lipar OH (nonionic surfactant, manufactured by Lion Corporation) to 100 parts of ice water, add 10.1 parts of cyanuric chloride after dissolution, and stir for 15 minutes. Next, 18.0 parts of 2,5-disulfoaniline monosodium salt (purity: 85.5%) was added at 8 to 10 ° C., and the pH was adjusted while dropping a 10% aqueous sodium carbonate solution at that temperature. The reaction solution containing the primary condensate of cyanuric chloride and 2,5-disulfoaniline is obtained by keeping the 2.7 to 3.0 and performing the primary condensation reaction for 4 hours.

  (3) No. obtained in (1) in the reaction solution of (2). Add 23.5 parts of compound 2 and warm. The reaction is carried out for 1 hour while maintaining the pH at 4.3 to 4.7 while dropping a 10% aqueous sodium carbonate solution dropwise at a temperature of 60 to 65 ° C. Next, after maintaining the pH at 7 to 7.2 for 30 minutes, a small amount of insoluble matter is filtered off. Water is added to the mother liquor to bring the liquid volume to 600 parts, and 72 parts of sodium chloride is added and stirred while heating and maintaining at 55-60 ° C. After 1 hour, the crystals were filtered off, washed with 75 parts of a 10% saline solution and dried. 33.2 parts of compound 3 are obtained as red crystals (salt content 33.7%, sodium nitrate content 0.1%).

  (4) No. obtained in (3) in a mixed solution of 400 parts of water and 400 parts of methanol. Add 10.0 parts of compound No. 3 and stir for 1 hour under reflux to dissolve, then cool with ice to precipitate bright red crystals. The mixture was stirred for 1 hour, filtered, washed with 100 parts of methanol and dried. 6.4 parts of desalted product of the compound of No. 3 are obtained (sodium content is 0.3%, sodium nitrate content is 0.1% or less). λmax: 526 nm (in aqueous solution)

  (5) No. Using a desalted product of compound 3, prepared an ink by an ordinary method, printed on an exclusive paper (made by Canon Inc.) with an inkjet printer, and measured the water resistance and light resistance of the recorded image. Was also good.

Example 2
(1) No. obtained in (1) of Example 1. 9 parts of the compound No. 3 is added to 180 parts of hot water at about 80 ° C., a 10% aqueous sodium hydroxide solution is added dropwise, and the reaction is carried out at 85 ° C. for 2 hours while maintaining the pH at 11. Next, after adjusting the liquid volume to 250 parts, 50 parts of sodium chloride is added at 55 to 60 ° C. and held at 55 to 60 ° C. for 2 hours. The precipitated crystals are filtered and dried. 7.6 parts of compound 4 are obtained as red crystals.

  (2) No. obtained in (1) in 100 parts of water. Add 4 parts of compound 4 and dissolve. Next, after adding 200 parts of methanol, it stirs at 50-55 degreeC for 1 hour. After filtration and drying, no. 3.3 parts of desalted product of compound 4 are obtained as red crystals. λmax: 526 nm (in aqueous solution)

  (3) No. Ink was prepared by the usual method using the desalted product of compound No. 4, printed on special paper (made by Canon Inc.) with an inkjet printer, and the water resistance and light resistance of the recorded image were measured. Was also good.

Example 3
(1) No. obtained in (1) of Example 1 11.7 parts of compound 2 are added to 125 parts of pyridine and heated to 80 ° C. 9.6 parts of p-toluenesulfonyl chloride are then added in about 10 minutes. After reacting at 100 ° C. for 2 hours, water cooling, filtration, washing with water and drying were carried out. 12.2 parts of 27 compounds are obtained as red crystals.

  (2) No. obtained in (1) in 200 parts of water. Add 6.0 parts of 27 compound, then add 2.4 parts of 24% caustic soda to pH 11.5 and stir for 1 hour. After adjusting the liquid volume to 300 parts, 22.5 parts of sodium chloride is added and stirred for 1 hour, followed by filtration to obtain 16 parts of a wet cake. The wet cake (16 parts) is heated and refluxed together with methanol (150 parts) and water (75 parts), and filtered after 1 hour to separate a small amount of insoluble matter. The mother liquor was stirred for 1 hour under ice-cooling, and the precipitated crystals were separated by filtration, washed with a small amount of methanol and dried. 4.0 parts of desalted product of 27 compounds are obtained as red crystals.

Example 4
(1) 30.9 parts of the compound of formula (3) (R ₁ = ethoxycarbonyl group, R ₂ = CH ₃ ), 15.5 parts of potassium carbonate, and acetic acid in 250 parts of N, N-dimethylformamide with stirring. Then, 9.0 parts of cupric monohydrate and 53.0 parts of 5-acetylamino-2-sulfoaniline are sequentially added, and the temperature is raised to 110 ° C. over 1 hour. The reaction is carried out at a temperature of 110 to 120 ° C. for 3 hours. It is then cooled and the reaction solution is poured into 2200 parts of water. Stir at 20 ° C. for 1 hour, then filter to remove a small amount of insolubles. Water is added to the mother liquor to make the liquid volume about 3000 parts, and 450 parts of sodium chloride is added with stirring. The crystals precipitated after stirring at room temperature for 1 hour were filtered and dried. 32.9 parts of 45 compounds are obtained as red crystals.

  (2) Into 145 parts of water, 156 parts of 96% sulfuric acid was added dropwise under cooling to prepare 50% sulfuric acid. 32.7 parts of 45 compounds are added. The temperature is raised to 75 ° C. over 1 hour, and the reaction is carried out at 75-80 ° C. for 10 hours. After cooling, the reaction solution is poured into 400 parts of ice water. Stir at 20 ° C. for 1 hour, then filter and dry. 25.4 parts of 46 compounds are obtained as red crystals.

  (3) No. 1 in 100 parts of pyridine. 10.4 parts of 46 compounds are added with stirring. The temperature is raised to 90 ° C., and 6.9 parts of p-toluenesulfonyl chloride is added over 30 minutes. The reaction is performed at a temperature of 90 to 100 ° C. for 3 hours. It is then cooled and filtered to remove a small amount of insoluble matter. The mother liquor was poured into 350 parts of 10% sulfuric acid, stirred for 1 hour at 20 ° C., and the precipitated crystals were filtered and dried. 13.5 parts of 36 compounds are obtained as red crystals.

Example 5
(1) Add 0.25 parts of Lipar OH to 100 parts of ice water, add 10.1 parts of cyanuric chloride after dissolution, and stir for 15 minutes. Next, 14.0 parts of 5-sulfoanthranilic acid (purity 88.4%) was added at 8 to 10 ° C., and the pH was adjusted to 2.7 to 3.0 while dropping a 10% aqueous sodium hydroxide solution at that temperature. And a primary condensation reaction is carried out for 3 hours to obtain a reaction liquid containing a primary condensate of cyanuric chloride and 5-sulfoanthranilic acid.

  (2) No. obtained in (1) of Example 1 in the reaction solution of (1) above. Add 23.5 parts of compound 2 and warm. At a temperature of 60 to 65 ° C., the pH is kept at 4.3 to 4.7 while dropping a 10% sodium hydroxide aqueous solution, and the reaction is carried out for 2 hours. Next, the solution is filtered to remove a small amount of insoluble matter and No. A reaction solution containing 15 compounds is obtained.

  (3) No. obtained in (2) above. Water is added to the reaction solution containing 15 compounds to make the volume 600 parts, and a 10% aqueous sodium hydroxide solution is added dropwise, and the reaction is carried out at 90 ° C. for 2 hours while maintaining the pH at 10.5. Next, after adjusting the liquid volume to 800 parts, concentrated hydrochloric acid is added dropwise at 55-60 ° C. to adjust the pH to 2.7, and the mixture is held at 55-60 ° C. for 1 hour. The precipitated crystals are filtered. The resulting wet cake is then heated with 500 parts of methanol under stirring and held at 60 ° C. for 1 hour. Next, filtration, washing with 100 parts of methanol, drying and No. 36.0 parts of desalted product of 16 compounds are obtained as red crystals. λmax: 520 nm (as an ammonium salt in an aqueous solution)

  (4) No. Ink was prepared by a normal method using a desalted product of 16 compounds, printed on a dedicated paper (manufactured by Seiko Epson) with an inkjet printer, and the water resistance and light resistance of the recorded image were measured. Both were good. Moreover, there was no discoloration by an alkali and it was favorable.

Example 6
(1) No. obtained in (1) of Example 1. Then, 10.0 parts of the compound No. 3 is added to 100 parts of hot water at about 85 ° C., then 10.0 parts of 28% aqueous ammonia is added, and the reaction is carried out at 80 to 90 ° C. for 4 hours under heating. (During that time the pH drops from 11.0 to 8.5.)
Next, 10.0 parts of 28% aqueous ammonia is added and the reaction is carried out at 85 ° C. for 3 hours. (In the meantime, the pH drops from 10.5 to 9.0.) Confirm that the reaction is complete by HPLC (high performance liquid chromatography). Next, 1.5 parts of pearlite (diatomaceous earth, Mitsui Kinzoku Co., Ltd.) is added, stirred at 60 to 65 ° C. for 15 minutes, and then filtered. Hot water is added to the mother liquor to adjust the liquid volume to 200 parts and then heated and maintained at 60-65 ° C. At that temperature, 30 parts of sodium chloride is added, and then concentrated hydrochloric acid is added to adjust the pH to 0.5 to precipitate crystals. After stirring for 30 minutes, it was filtered and No. A wet cake of 5 compounds is obtained. Next, after washing with 150 parts of methanol and drying, No. 6.0 parts of compound 5 are obtained as red crystals. λmax: 523 nm (as an ammonium salt in an aqueous solution)
(2) No. Ink was prepared by the usual method using compound No. 5, printed on special paper (Seiko-Epson) with an inkjet printer, and the water resistance and light resistance of the recorded image were measured. there were.

Example 7
(1) No. obtained in (1) of Example 1. The reaction solution containing the compound No. 3 is heated to 85 ° C., and a 10% caustic soda aqueous solution is added dropwise with stirring to carry out the reaction at 85 ° C. for 2 hours while maintaining the pH at 11. Next, 8.0 parts of pearlite is added, and the mixture is stirred for 10 minutes and filtered. Concentrated hydrochloric acid is added to the mother liquor, the pH is adjusted to 6-7, and then heated and maintained at 60-65 ° C., 80 parts of sodium chloride is added and stirred for 30 minutes for salting out. The resulting crystals are filtered and washed with 40 parts of a 20% saline solution. Concentrated hydrochloric acid is added dropwise over 1 hour and 30 minutes while heating the obtained wet cake together with 400 parts of water and kept at 60 to 65 ° C., and the pH is adjusted to 0.8 to precipitate crystals. After stirring for 30 minutes, the mixture was filtered. A wet cake of 4 compounds is obtained.
(2) The wet cake obtained in (1) is heated together with 300 parts of methanol and stirred at 60 to 65 ° C. for 1 hour. Subsequently, the mixture was filtered, washed with 200 parts of methanol, dried, and No. 31.3 parts of a desalted product of compound 4 are obtained as red crystals.
(3) No. After adding ammonia to the ammonium salt by a conventional method using a desalted product of compound No. 4, ink is prepared, printed on special paper (made by Canon Inc.) with an ink jet printer, and water resistance of the recorded image When the properties and light resistance were measured, both were good.

Example 8
(1) Preparation of Ink No. obtained in Example 2 An ink composition having the composition shown in the following Table 2 including a salt obtained by desalinating the 4 anthrapyridone compound was prepared, and filtered through a 0.45 μm membrane filter to obtain the ink jet ink of the present invention.

Table 2 Composition of ink Dye (No. 4) 7 parts Water 73 parts Glycerin 5 parts Urea 5 parts N-methyl-2-pyrrolidone 5 parts Ethylene glycol 5 parts Total 100 parts

In the above, no. In place of the 4 anthrapyridone compounds (pigments), C.I. I. A comparative inkjet ink composition was prepared using Acid Red 37 in the same manner as described above.
(2) Inkjet printing Using an inkjet printer (BJF-600, manufactured by Canon Inc.), inkjet recording was performed on commercially available glossy paper (Color BJ Photosheet Film CA-101, manufactured by Canon Inc.).
(3) Hue and sharpness of recorded image: Color measurement was performed on a printed recording paper (GREATAG SPM50: manufactured by GREATAG), and L *, a *, and b * values were calculated. The hue was compared with the standard colorimetric value of the standard magenta of Japan Color of JNC (Japan Printing Industrial Machinery Manufacturers Association). The sharpness C * was calculated by the following formula (1). The results are shown in Table 3.

(4) Light resistance test of recorded image Using a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.), the recorded image was irradiated for 20 hours. Judgment grade was judged according to the grade of blue scale prescribed in JIS L-0842.
(5) Water resistance test of recorded images Printed recording material is placed in a container of saturated steam at 100 ° C for 60 minutes, and the effect of water (steam) (the state of bleeding from the printed part to the unprinted part) ) Was evaluated. The evaluation results are indicated by the following symbols.
○ No blades at all
△ Medium grade blade
X Extremely large blades are observed Table 3 summarizes the test results (1) to (5).

Table 3
Hue Sharpness Light resistance Water resistance
L * a * b * (C *) (Class) Judgment
JNC standard magenta 46.3 74.4 -4.8 74.5 − −
No. 2 in Example 2. 4 48.4 81.0 -3.9 81.1 Grade 4 ○
Ink for comparison 48.3 78.2 24.0 81.8 Grade 4 ×

  From the results in Table 3, it can be seen that the ink composition of the present invention has a value approximate to JNC standard magenta, and is suitable as a magenta ink for ink jet. In addition, since it is remarkably excellent in water resistance, durability in a high humidity environment is excellent.

Example 9
The following tests were carried out using the following ink compositions.
(1) Used ink composition Magenta ink
M1: No. obtained in Example 2 4 Ink composition
M2: Ink composition for comparison control Cyan ink
C1: C.I. I. Cyan ink composition containing Direct Bull-199 (copper phthalocyanine dye) (2) Inkjet print
Using an inkjet printer, magenta ink alone and cyan ink and magenta ink were overlaid on glossy paper (Canon, color BJ photosheet film CA-101) having a dye-receiving layer to obtain an inkjet print. .

(3) Light Resistance Test of Recorded (Printed) Image Using an accelerated xenon light resistance tester manufactured by Wacom, the recording paper printed in the above (2) was subjected to a light resistance test for 40 hours. The light fastness of the printed image printed on top of each other was excellent.
(4) Color measurement The hue of the recorded images before and after the light resistance test was measured using the colorimeter, and the color difference (ΔE) was determined. The results are shown in Table 4.

Table 4
Printing method Glossy paper (ΔE)
1 (M1 alone) 16.5
2 (printed with C1 over M1) 15.4
3 (M2 alone) 10.3
4 (Printed with C1 over M2) 24.5

  Comparing the blue (magenta + cyan) 2 printed with multiple printing (overprinting) and the comparative control 4, 2 (the present invention) has a small ΔE and is clearly superior. A combination of a cyan ink composed of a water-soluble copper phthalocyanine dye and a conventional magenta ink has a large discoloration and causes a problem in use. As described above, the magenta ink of the present invention has a good balance and small discoloration even in combination with a cyan ink, and a printed image having excellent durability can be obtained because the light resistance of an image printed in a superimposed manner is good.

Example 10
In accordance with Example 8, the following Y: yellow, M: magenta, C: cyan inks were prepared, mixed colors were printed, the obtained recorded images were evaluated, and each color standard colorimetry of the aforementioned Japan Color. Compared with value. The obtained results are shown in Table 4, and the color space is shown in FIG.
Dye used for ink preparation Y: C.I. I. Direct yellow-86
M: No. obtained in Example 2 Dye 4 C: C.I. I. Direct Bull-199

Table 5
JNC Standard Dye Dye when using the ink of the present invention
a * b * a * b *
Yellow-6.6 91.1 12.9 107.8
Red 68.5 48.1 68.2 59.3
Magenta 74.4 -4.8 81.0 -3.9
Bull-20.0-51.0 26.9-53.5
Cyan -37.5 -50.4 -41.3 -48.3

As is apparent from the results in Table 5, when the ink of the present invention is used, a hue and a mixed hue approximate to the JNC standard hue can be obtained by a combination of magenta ink, yellow ink and cyan ink. The magenta dye of the present invention is very useful industrially for inkjet printing.

FIG. 1 is an example showing the range of color development by an anthrapyridone compound of the present invention and a comparative dye.

Explanation of symbols

  In FIG. 1, the X axis indicates the a * value in the L * a * b * color system, and the Y axis also indicates the b * value. Y is yellow, R is red, M is magenta, B is blue, C is cyan, and G is green. The solid line is the color development range of the compound of Example 2, and the broken line is the standard colorimetric value of Japan Color. The plot of G by the solid line is C.I. I. Direct Yellow-86 and C.I. I. This is a color generation (reference value) by direct bull-199 overstrike.

Claims (15)

Formula AB
(In the formula, A represents the following formula (1)

(Wherein R ₁ represents a hydrogen atom, an alkoxycarbonyl group or a benzoyl group, and R ₂ represents a hydrogen atom or a methyl group.)
And B represents a hydrogen atom or a substituent on the dye residue A. )
An anthrapyridone compound or a salt thereof B is an acyl group or the following formula (2)

(Wherein X and Y are each independently a chlorine atom, hydroxyl group, amino group, monoethanolamino group, diethanolamino group, morpholino group, or anilino group (from sulfonic acid group, carboxyl group, methyl group, chlorine atom) It may be substituted with one or two or more selected substituents.)
An anthrapyridone compound or a salt thereof according to claim 1, which is a group represented by the formula: 3. In the formula (2) of claim 2, X is an anilino group (which may be substituted with one or two substituents selected from a sulfonic acid group and a carboxyl group), Y is a chlorine atom, a hydroxyl group, an amino group An anthrapyridone compound or a salt thereof according to claim 2, which is a monoethanol group, a diethanol group or a morpholino group. The anthrapyridone compound or a salt thereof according to claim 2, wherein the acyl group is a benzenesulfonyl group, a tosyl group, a 2-carboxy-benzoyl group, or a 3,4-dicarboxybenzoyl group. The anthrapyridone compound or a salt thereof according to claim 1, wherein R ₁ is a hydrogen atom, and R ₂ is a methyl group. An aqueous magenta ink composition comprising the anthrapyridone compound or a salt thereof according to claim 1 as a pigment component. The aqueous magenta ink composition according to claim 6, comprising water and an organic solvent. The aqueous magenta ink composition according to claim 6 or 7, wherein the content of the inorganic salt in the anthrapyridone compound or a salt thereof is 1% by weight or less. The aqueous magenta ink composition according to any one of claims 6 to 8, which is for inkjet recording. 9. An ink jet recording method for recording on a recording material by ejecting ink droplets according to a recording signal, wherein the water-based magenta ink composition according to any one of claims 6 to 8 is used as ink. Inkjet recording method In an ink jet recording method for recording on a recording material by ejecting ink droplets according to a recording signal, the water-based magenta ink composition according to any one of claims 6 to 8 is used as a magenta ink and water-soluble as a cyan ink. Inkjet recording method characterized by using water-based ink containing metal phthalocyanine dye 12. The inkjet recording method according to claim 11, wherein the recording material is an information transmission sheet. 13. The ink jet recording method according to claim 12, wherein the information transmission sheet is a surface-treated sheet. An ink jet printer having a container containing the aqueous magenta ink composition according to any one of claims 6 to 8 and a container containing an aqueous cyan ink composition containing a water-soluble metal phthalocyanine dye. The anthrapyridone compound or a salt thereof according to claim 1, wherein R ₁ is a hydrogen atom or a lower alkoxycarbonyl group, R ₂ is a methyl group, B is a hydrogen atom or a C _{1 to} C ₄ alkoxycarbonyl group.

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