JP2005008868A - Anthrapyridone compound, aqueous magenta ink composition, and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magenta dyestuff having a hue and clarity suitable for inkjet recording and capable of giving excellent fastness, such as light resistance, gas resistance, and water resistance, to recorded matter. <P>SOLUTION: An anthrapyridone compound expressed by formula (1), or its salt, and an aqueous magenta ink composition containing the same are provided, respectively. <P>COPYRIGHT: (C)2005,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 ink jet printer recording methods, all of which generate ink droplets and attach them to various recording materials (paper, film, fabric, etc.) for recording It is. The recording method using an ink jet printer is characterized by the fact that the recording head does not come into contact with the recording material, so that no mechanical noise is generated, and the printer can be easily reduced in size, increased in speed, and colored. Widespread and is expected to grow significantly in the future. In order to record an image or character information on a color display of a computer in color by an ink jet printer, generally, four colors of ink of yellow (Y), magenta (M), cyan (C), and black (K) are used. Expressed in subtractive color mixing. In order to reproduce the additive color mixture image by R, G, B such as a CRT display as faithfully as possible by the subtractive color mixture image, the dyes used, particularly the dyes used for the Y, M, and C inks, are Y, M as much as possible. , C are desired to have a hue close to the respective standards and 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, light resistance and gas resistance.

  Applications of inkjet printers are expanding from small OA printers to large industrial printers, and fastnesses such as water resistance and light resistance are required more than ever. Water resistance has been greatly improved by coating the surface of paper with PVA resin and other inorganic fine particles capable of adsorbing pigments such as porous silica, cationic polymers, alumina sol or special ceramics. There are demands for further strict quality improvements such as improved moisture resistance during storage of printed materials. In addition, the technology for greatly improving the light resistance has not been established yet, and in particular, among the four primary colors Y, M, C, and K, many of the magenta dyes originally have low light resistance, and the improvement is important. It has become a challenge.

Examples of the dye skeleton of the magenta dye used in the water-soluble ink for ink-jet recording include xanthene-based and azo-based using H acid. However, xanthene dyes have very good hue and sharpness but very poor light resistance. Also, some azo dyes using H acid are good in terms of hue and water resistance, but are inferior in light resistance and sharpness. In this type, a magenta dye excellent in sharpness and light resistance has also been developed, but the light resistance is still inferior to other hue dyes such as cyan and yellow dyes typified by copper phthalocyanine dyes.
With the recent penetration of digital cameras, the opportunity to print photos at home is also increasing. When storing this photograph, discoloration of the photograph quality due to the oxidizing gas in the air is regarded as a problem.

  As a magenta dye skeleton having excellent sharpness and light resistance, there are anthrapyridone dyes (for example, see Patent Documents 1 to 7), but hue, sharpness, light resistance, water resistance, gas resistance, and dissolution stability are excellent. There is nothing to satisfy everything.

JP 59-74173 A (page 1-3) Japanese Patent Laid-Open No. 2-16171 (pages 1 and 5-7) JP 2000-109464 A (pages 1-2 and 8-12) JP 2000-169776 A (pages 1-2, 6-9) JP 2000-191660 A (pages 1-3 and 11-14) JP 2001-72884 A (pages 1-2 and 8-11) JP 2001-139836 A1 (pages 1-2 and 7-12)

  An object of the present invention is to provide a magenta dye having a hue and sharpness suitable for ink jet recording and excellent in light fastness, gas fastness and moisture fastness of recorded matter.

（式（１）中、Ｒ₁は水素原子、アルキル基、ヒドロキシ低級アルキル基、シクロヘキシル基、モノ若しくはジアルキルアミノアルキル基又はシアノ低級アルキル基を、Ｘはスルホン酸基、メトキシ基、アニリノ基、フェノキシ基で置換されていてもよいアニリノ基；メチル−スルホアニリノ基；メトキシ−スルホアニリニノ基；カルボキシ−スルホアニリノ基；カルボキシ−ヒドロキシアニリノ基；スルホン酸基で置換されていてもよいナフチルアミノ基；スルホン酸基、カルボキシ基、水酸基で置換されていてもよいモノ若しくはジアルキルアミノ基；アラルキルアミノ基；シクロアルキルアミノ基；スルホン酸基、カルボキシル基、アセチルアミノ基、アミノ基、水酸基又、フェノキシ基又はフェニル基で基で置換されていてもよいフェノキシ基；モノアルキルアミノアルキルアミノ基；ジアルキルアミノアルキルアミノ基；水酸基又はアミノ基を、Ｙは塩素原子、水酸基、アミノ基、モノ若しくはジアルキルアミノ基（アルキル基上にスルホン酸基、カルボキシ基および水酸基からなる群から選択される置換基を有してもよい）又はモルホリノ基をそれぞれ表す））
で表されるアントラピリドン化合物又はその塩、
（２）式（１）におけるＲ₁がメチル基である（１）に記載のアントラピリドン化合物又はその塩、
（３）式（１）におけるＹが水酸基又はアミノ基である（１）または（２）に記載のアントラピリドン化合物又はその塩、
（４）式（１）におけるＸが、アニリノ基、２−スルホアニリノ基、２，５−ジスルホアニリノ基、２−エチルヘキシルアミノ基又はシクロヘキシルアミノ基、４−メトキシ−２−スルホアニリノ基、２−カルボキシ−５−スルホアニリノ基、３−カルボキシ−４−ヒドロキシアニリノ基である請求項１から３のいずれか一項に記載のアントラピリドン化合物又はその塩、
（５）色素成分として、（１）から（４）のいずれか一項に記載のアントラピリドン化合物又はその塩を含むことを特徴とする水性マゼンタインク組成物、
（６）水溶性有機溶剤を含有する（５）に記載の水性マゼンタインク組成物、
（７）アントラピリドン化合物又はその塩中の無機塩の含有量が１質量％以下である（５）又は（６）に記載の水性マゼンタインク組成物、
（８）インクジェット記録用である（５）から（７）のいずれか一項に記載の水性マゼンタインク組成物、
（９）インク滴を記録信号に応じて吐出させて被記録材に記録を行うインクジェット記録方法において、インクとして（５）から（７）のいずれか一項に記載の水性マゼンタインク組成物を使用することを特徴とするインクジェット記録方法
（１０）被記録材が情報伝達用シ−トである（９）に記載のインクジェット記録方法、
（１１）（５）から（７）のいずれか一項に記載の水性マゼンタインク組成物を含有する容器、
（１２）（１１）の容器を有するインクジェットプリンタ、
（１３）（１）から（４）のいずれか一項に記載のアントラピリドン化合物又はその塩を有する着色体、
に関する。 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 (1)

(In the formula (1), R ₁ represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a mono- or dialkylaminoalkyl group or a cyano lower alkyl group, and X represents a sulfonic acid group, a methoxy group, an anilino group, or a phenoxy group. An anilino group optionally substituted with a group; a methyl-sulfoanilino group; a methoxy-sulfoanilino group; a carboxy-sulfoanilino group; a carboxy-hydroxyanilino group; a naphthylamino group optionally substituted with a sulfonic acid group; A mono- or dialkylamino group optionally substituted by a carboxy group or a hydroxyl group; an aralkylamino group; a cycloalkylamino group; a sulfonic acid group, a carboxyl group, an acetylamino group, an amino group, a hydroxyl group, a phenoxy group or a phenyl group A group optionally substituted with a group Noxy group; monoalkylaminoalkylamino group; dialkylaminoalkylamino group; hydroxyl group or amino group, Y represents chlorine atom, hydroxyl group, amino group, mono- or dialkylamino group (sulfonic acid group, carboxy group and hydroxyl group on the alkyl group) Which may have a substituent selected from the group consisting of: or a morpholino group)))
An anthrapyridone compound represented by
(2) An anthrapyridone compound or a salt thereof according to (1), wherein R ₁ in formula (1) is a methyl group,
(3) An anthrapyridone compound or a salt thereof according to (1) or (2), wherein Y in formula (1) is a hydroxyl group or an amino group,
(4) X in the formula (1) is an anilino group, 2-sulfoanilino group, 2,5-disulfoanilino group, 2-ethylhexylamino group or cyclohexylamino group, 4-methoxy-2-sulfoanilino group, 2-carboxy-5. An anthrapyridone compound or a salt thereof according to any one of claims 1 to 3, which is a -sulfoanilino group or a 3-carboxy-4-hydroxyanilino group;
(5) A water-based magenta ink composition comprising the anthrapyridone compound or a salt thereof according to any one of (1) to (4) as a dye component,
(6) The aqueous magenta ink composition according to (5), which contains a water-soluble organic solvent,
(7) The aqueous magenta ink composition according to (5) or (6), wherein the content of the inorganic salt in the anthrapyridone compound or a salt thereof is 1% by mass or less,
(8) The aqueous magenta ink composition according to any one of (5) to (7), which is for inkjet recording.
(9) In an ink jet recording method in which ink droplets are ejected in accordance with a recording signal to perform recording on a recording material, the water-based magenta ink composition according to any one of (5) to (7) is used as ink. (10) The inkjet recording method according to (9), wherein the recording material is a sheet for information transmission,
(11) A container containing the aqueous magenta ink composition according to any one of (5) to (7),
(12) An inkjet printer having the container of (11),
(13) A colored product having the anthrapyridone compound or a salt thereof according to any one of (1) to (4),
About.

  The novel anthrapyridone compound of the present invention is extremely excellent in water solubility, its aqueous solution has good stability over time, and has good characteristics of filterability with respect to a membrane filter in the process of producing an ink composition. Furthermore, this compound has high safety for living bodies. Furthermore, the ink composition of the present invention using this novel anthrapyridone compound is free from crystal precipitation, physical property change, color change and the like after long-term storage, and has good storage stability. In addition, a printed matter using the ink composition of the present invention as a magenta ink for ink jet recording is excellent in light resistance, ozone resistance and moisture resistance, and can perform excellent ink jet recording. Furthermore, the printing surface is clear and has an ideal magenta color, and when used with other yellow and cyan inks, a color tone in a wide visible region can be produced. Thus, the ink composition of the present invention is extremely useful as a magenta ink for inkjet recording.

The present invention will be described in detail. The anthrapyridone compound or a salt thereof of the present invention is represented by the formula (1).
In the formula (1), R ₁ represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a mono- or dialkylaminoalkyl group, or a cyano lower alkyl group. Examples of the alkyl group in the present invention include 1 to C carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, an n-hexyl group, and an n-octyl group. 8 alkyl groups and the like.
In addition, examples of the lower alkyl group in the present invention include those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms among the above alkyl groups, and more preferably a methyl group, an ethyl group or a propyl group. Can be mentioned. The same applies to cases other than the lower alkyl group in the present invention, such as “lower” in a lower alcohol.
Examples of the hydroxy lower alkyl group in R ₁ include a hydroxyethyl group and a hydroxypropyl group. Examples of the monoalkylaminoalkyl group include a methylaminopropyl group and an ethylaminopropyl group. Examples of the alkyl group include a dimethylaminopropyl group and a diethylaminoethyl group. Examples of the cyano lower alkyl group include a cyanoethyl group and a cyanopropyl group. Preferable R ₁ includes a hydrogen atom and a lower alkyl group, more preferably a hydrogen atom and a methyl group, and particularly preferably a methyl group.

Specific examples of the anilino group optionally substituted with a sulfonic acid group, a carboxy group, a methyl group, a methoxy group, an anilino group, or a phenoxy group in X of the formula (1) include, for example, anilino, 2-sulfoanilino, 3-sulfoanilino 4-sulfoanilino, 2,5-disulfoanilino, 4-methoxy-2-sulfoanilino, 4-methyl-2-sulfoanilino, 2-methyl-4-sulfoanilino, 2-carboxy-5-sulfoanilino, 2-carboxy-4-sulfoanilino 4-anilino-3-sulfoanilino, 4-methoxy-2-sulfoanilino, 2-carboxy-5-sulfoanilino, 3-carboxy-4-hydroxyanilino, 4-phenoxyanilino, etc., and substituted with a sulfonic acid group Specific examples of naphthylamino that may be used include 1-naphthylamino group, 4-sulfo-1-naphthylamino, 5-sulfo-1-naphthylamino, 5-sulfo-2-naphthylamino, 6-sulfo-1-naphthylamino, 7-sulfo-1-naphthylamino 4,8-disulfo-2-naphthylamino, 3,8-disulfo-1-naphthylamino, 3,6-disulfo-1-naphthylamino, 3,6,8-trisulfo-2-naphthylamino, 4,6 , 8-trisulfo-2-naphthylamino, 3,6,8-trisulfo1-naphthylamino and the like, and specific examples of the monoalkylamino group optionally substituted with a sulfonic acid group, a carboxy group, or a hydroxyl group For example, methylamino, ethylamino, propylamino, butylamino, 2-ethylhexylamino, 2-sulfoethylamino, 2-carboxyethyl Amino, 1,2-dicarboxyethylamino, 1,3-dicarboxypropylamino, 2-hydroxyethylamino, cyclohexylamino and the like, and dialkylamino optionally substituted with a sulfonic acid group, a carboxy group or a hydroxyl group Specific examples of the group include dimethylamino, diethylamino, dipropylamino, dibutylamino, bis (carboxymethyl) amino, bis (2-hydroxyethyl) amino and the like. Specific examples of the aralkylamino group include, for example, Specific examples of the cycloalkylamino group include cyclohexylamino, which may be substituted with a sulfonic acid group, a carboxyl group, an acetylamino group, an amino group, a hydroxyl group, a phenoxy group, or a phenyl group. As a specific example of a good phenoxy group Examples include phenoxy, 4-sulfophenoxy, 4-carboxyphenoxy, 4-acetylaminophenoxy, 4-hydroxyphenoxy, 4-phenoxyphenoxy, 4- (4-carboxyphenoxy) phenoxy, 4-phenylphenoxy and the like. Specific examples of the monoalkylaminoalkylamino group include 2-methylamino-ethylamino, 3-methylamino-propylamino, 3-ethylamino-propylamino and the like, and specific examples of the dialkylaminoalkylamino group Examples thereof include 3- (N, N-diethylamino) propylamino and 2- (N, N-diethylamino) ethylamino. X is 2-sulfoanilino, 2,5-disulfoanilino, 4-methyl-2-sulfoanilino, 2-methyl-4-sulfoanilino, 4-methoxy-2-sulfoanilino, 2-carboxy-5-sulfoanilino, 2-carboxy-4- Sulfoanilino is preferred, and 2-sulfoanilino, 2,5-disulfoanilino, 2-carboxy-5-sulfoanilino and 2-carboxy-4-sulfoanilino are particularly preferred.
Y in the formula (1) is chloro, hydroxy, amino, 2-sulfoethylamino, 2-carboxyethylamino, carboxymethylamino, 1,2-dicarboxyethylamino, 1,3-dicarboxypropylamino, 2 -Hydroxyethylamino, 3- (N, N-diethylamino) propylamino, 2- (N, N-diethylamino) ethylamino, bis (carboxymethyl) amino, morpholino and the like, hydroxy, amino, 2-sulfoethyl Amino, 2-carboxyethylamino, carboxymethylamino, 3- (N, N-diethylamino) propylamino, 2- (N, N-diethylamino) ethylamino and bis (carboxymethyl) amino are preferred, especially hydroxy and amino. preferable.

Preferable combinations of R ₁ , X, and Y include, for example, R ₁ is a hydrogen atom or a methyl group, X is anilino, 2-sulfoanilino, 2,5-disulfoanilino 4-methoxy-2-sulfoanilino, 2-carboxy-5 Sulfoanilino, 3-carboxy-4-hydroxyanilino group, 2-ethylhexylamino or cyclohexylamino, Y is a hydroxyl group or an amino group, and the like.

  Specific examples of the anthrapyridone compound represented by the formula (1) of the present invention are shown in Table 1. In Table 1, (S) means a sulfonic acid group, 2 (S) means a disulfonic acid group, and (K) means a carboxy group.

Table 1
No. R ₁ X Y
1 CH3 2,5-2 (S) -anilino OH
2 CH3 2,5-2 (S) -anilino NH2
3 CH3 2,5-2 (S) -anilino monoethanolamino 4 CH3 2,5-2 (S) -anilino diethanolamino 5 CH3 anilino OH
7 CH3 Anilino Carboxyethylamino 8 H Anilino Sulfoethylamino 9 CH3 Benzylamino OH
10 CH3 cyclohexylamino OH
11 CH3 cyclohexylamino cyclohexylamino 12 CH3 n-butylamino OH
13 CH3 N, N-diethylpropylamino OH
14 CH3 N, N-diethylpropylamino N, N-diethylpropylamino 16 CH3 anilino N, N-diethylpropylamino 17 CH3 4-phenylphenoxy OH
18 CH3 4-Phenylphenoxy NH2
19 CH3 3-Amino-anilino OH
20 CH3 Anilino NH2
21 CH3 NH2 NH2
22 CH3 2-ethylhexylamino OH
23 CH3 2-ethylhexylamino NH2
24 CH3 2-ethylhexylamino 2-ethylhexylamino 25 CH3 2-ethylhexylamino morpholino 26 CH3 2-ethylhexylamino Cl
27 CH3 3- (S) -anilino OH
28 CH3 3- (S) -anilino NH2
29 CH3 3- (S) -anilino monoethanolamino 30 C2H5 3- (S) -anilino carboxyethylamino 31 CH3 3- (S) -anilino sulfoethylamino 32 CH3 2- (S) -anilino OH
33 CH3 2- (S) -anilino NH2
34 C2H4OH 2- (S) -anilino 2-ethylhexylamino 35 CH3 2- (S) -anilino morpholino 36 CH3 4-methoxy-2- (S) -anilino OH
37 C4H9 4-Methoxy-2- (S) -anilino NH2
38 CH3 2- (K) -5- (S) -anilino OH
39 CH3 2- (K) -4- (S) -anilino OH
40 CH3 4- (S) -naphthyl-1-ylamino OH

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

(Wherein R ₁ represents the same meaning as described above.)
1 obtained by reacting 1 mol of the above compound with 1 to 1.3 mol of 2,4,6-trichloro-S-triazine (cyanuric chloride) in water at pH 2 to 7, 5 to 35 ° C. for 2 to 8 hours. Formula (4) which is a secondary condensate

(Wherein R ₁ has the same meaning as described above)
Is reacted with 1 mol of an amine corresponding to X in the formula (1) at a pH of 4 to 9, 5 to 90 ° C. for 10 minutes to 5 hours, whereby Y is a chlorine atom.

(Wherein R ₁ and X have the same meaning as described above)
Is obtained as a secondary condensate.
It is then hydrolyzed at pH 9-12, 50-100 ° C., 10 minutes-5 hours, or reacted with ammonia, the corresponding amines at pH 8-10, 50-100 ° C., 10 minutes-8 hours. Formula (6) in which Y is not a chlorine atom as a secondary condensate

(Wherein R ₁ , X and Y have the same meaning as described above)
Is obtained.
The order of condensation is appropriately determined according to the reactivity of various compounds, and is not limited to the above.

The compound thus obtained exists in the form of the free acid or in the form of its salt. In the present invention, the free acid or a salt thereof can be used as an alkali metal salt, alkaline earth metal salt, alkylamine salt, alkanolamine salt or ammonium salt. 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, ammonium Salt. As a method for preparing the salt, for example, sodium salt is added to the reaction solution of the tertiary condensate obtained above, salted out and filtered to obtain a sodium salt as a wet cake, and the wet cake is dissolved again in water. If crystals obtained by adding hydrochloric acid to adjust the pH to 1 to 2 are filtered, they can be obtained in the form of a free acid (or a part of it as a sodium salt). Furthermore, while the wet cake in the form of the free acid is stirred with water, for example, potassium hydroxide, lithium hydroxide, or aqueous ammonia is added to make it alkaline, thereby obtaining potassium salt, lithium salt, and ammonium salt, respectively. .
In addition, the anthrapyridone compound of Formula (3) is obtained as follows, for example. That is, the following formula (7)

(Wherein R ₁ represents the same meaning as described above)

1 to 3 moles of anthraquinone compound represented by formula (1) to 3 moles in a polar solvent such as xylene in the presence of a basic compound such as sodium carbonate at 130 to 180 ° C. for 5 to 15 hours, Following formula (8)

(Wherein R ₁ represents the same meaning as described above)
Is obtained.

  Subsequently, 1 mol of metaaminoacetanilide is added to 1 mol of the compound of the formula (8), a base such as sodium carbonate and a copper catalyst such as copper acetate in an aprotic polar organic solvent such as N, N-dimethylformamide. In the presence of benzene, condensation is carried out by carrying out Ullmann reaction at 110 to 150 ° C. for 2 to 6 hours.

(Wherein R ₁ represents the same meaning as described above)
Is obtained.

  Next, the compound of formula (9) is sulfonated and hydrolyzed at 50-120 ° C. in 8-15% fuming sulfuric acid at a general formula (3).

(Wherein R ₁ represents the same meaning as described above)
The anthrapyridone compound is obtained.

Various anthrapyridone compounds or salts thereof represented by the formula (1) of the present invention can be used as magenta for coloring, and are particularly preferable as a coloring matter for ink. When used for ink, the compound is preferably a water-soluble salt.
The aqueous magenta ink composition of the present invention (hereinafter also simply referred to as ink in some cases) comprises a compound represented by the above formula (1) or a salt thereof (hereinafter sometimes referred to as a compound represented by the formula (1) or a salt thereof. The composition simply contains the dye of formula (1) as a dye component, and the composition contains water in the dye and, if necessary, water containing a soluble organic solvent (including a solubilizing agent; the same shall apply hereinafter). In some cases, it can be obtained by simply dissolving in an aqueous solvent). 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 small content of inorganic substances such as metal cation chlorides and sulfates. The total content of sodium chloride and sodium sulfate is 1% by mass or less. In order to produce the pigment component of the present invention with a small amount of inorganic substances, for example, a usual method using a reverse osmosis membrane or a dried product or wet cake of the pigment component of the present invention is stirred in a mixed solvent of methanol and water as many times as necessary. What is necessary is just to repeat operation which desalinates by the method of filtering and drying.

In an ink jet printer, for the purpose of supplying a high-definition image, two types of inks of high density ink and low density ink are set for cyan ink and magenta ink. In that case, it can be used as an ink set in which a high concentration ink containing the compound of the formula (1) of the present invention and a low concentration ink containing the compound of the formula (1) of the present invention are used in combination. In addition, a known magenta dye may be used in combination with the dye of the formula (1) having the above conditions.

The ink of the present invention is prepared using water as a medium as described above. In the ink of the present invention, the dye of the formula (1) obtained as described above is usually contained in an amount of 0.3 to 8% by mass. The balance is water and a water-soluble organic solvent and other ink preparation agents blended as necessary. Ingredients blended as necessary other than water may be contained within a range that does not impair the effects of the present invention. Water-soluble organic solvents are used as dye solubilizers, drying inhibitors (wetting agents), viscosity modifiers, penetration enhancers, surface tension modifiers, antifoaming agents, and the like. Other ink preparation agents include, for example, antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventing agents, UV absorbers, viscosity adjusting agents, dye dissolving agents, antifading agents, emulsion stabilizers, surface tension adjusting agents. , Known additives such as an antifoaming agent, a dispersing agent, and a dispersion stabilizer. The content of the water-soluble organic solvent is usually 0 to 60% by mass, preferably 10 to 50% by mass, and other ink preparation agents are usually used in an amount of 0 to 20% by mass, preferably 0 to 15% by mass, based on the whole ink. Is good.

Examples of the water-soluble organic solvent include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol, N, N-dimethylformamide or N, N Carboxylic acid amides such as dimethylacetamide, preferably lower alkylamides of lower aliphatic carboxylic acids, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethyl Heterocyclic ketones such as hexahydropyrimido-2-one, preferably 5- or 6-membered cyclic ketones containing nitrogen atoms, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one Or a keto alcohol, preferably an aliphatic ketone having 1 to 8 carbon atoms Or cyclic ethers such as ketoalcohol, tetrahydrofuran, dioxane, etc., preferably cyclic ethers having 1 to 8 carbon atoms, ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol , 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc., monomers, oligomers or poly (C2) having an (C2-C6) alkylene unit To C6) polyol (triol) such as alkylene glycol or thioglycol, glycerin or hexane-1,2,6-triol, preferably aliphatic triol having 3 to 8 carbon atoms, ethylene glycol (C1-C4) alkyl ethers of lower polyhydric alcohols such as monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, γ-butyrolactone or dimethyl Examples thereof include sulfoxide.

Of these, preferred are isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone and N-methyl-2-pyrrolidone, more preferably isopropanol, glycerin, diethylene glycol and 2-pyrrolidone. is there. 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, benzthiazole, nitrityl, pyridine, 8- Oxyquinoline, benzothiazole, isothiazoline, dithiol, pyridine oxydide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, Examples thereof include brominated indanone compounds, benzyl bromoacetate compounds, and inorganic salt compounds. An example of the organic halogen compound is sodium pentachlorophenol, an example of the pyridine oxido compound is sodium 2-pyridinethiol-1-oxide, and an example of the inorganic salt compound is anhydrous sodium acetate. Examples of the isothiazoline-based compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Can be mentioned. Other antiseptic / antifungal agents include sodium sorbate, sodium benzoate, and the like (for example, Proxel GXL (S), Proxel XL-2 (S), etc. manufactured by Avecia).

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

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, and dicyclohexylammonium nitrite.

Examples of the ultraviolet absorber include a compound that emits fluorescence by absorbing ultraviolet rays typified by benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, or benzoxazole compounds, so-called fluorescence. Brighteners can also be used.
Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like.

The anti-fading agent is used for the purpose of improving image storage stability. As the antifading agent, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like.

Examples of the surface tension adjusting agent include a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant. Anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfates polyoxyalkyl ether sulfates Salt, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkylphenol type phosphate ester, alkyl type phosphate ester, alkyl allyl sulfone hydrochloride, diethyl sulfosuccinate, Examples thereof include dioctyl sulfosuccinate and the like. Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives. Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ethers such as alkyl ethers, polyoxyallylalkyl alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquis Esters such as oleate, polyoxyethylene monooleate, polyoxyethylene stearate, 2, 4, 7, -Acetylene glycol systems such as tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol (for example, Nissin Chemical's Surfinol 104E, 104PG50, 82, 465, Olphine STG, etc.). These ink preparation agents are used alone or in combination. The surface tension of the ink of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m. The viscosity of the ink of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less.
The aqueous ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order. The obtained ink composition may be filtered with a membrane filter or the like in order to remove impurities.

  The recording material in the inkjet recording method of the present invention is not particularly limited as long as it is a material that can be recorded by inkjet. Examples thereof include information transmission sheets such as paper and film, fibers and leather. The information transmission sheet is preferably a surface-treated sheet, specifically, an ink receiving layer provided on these substrates. For example, the ink receiving layer may be formed by impregnating or coating the base material with a cationic polymer, or by adsorbing inorganic fine particles capable of adsorbing pigments in ink such as porous silica, alumina sol, and special ceramics, such as polyvinyl alcohol and polyvinyl pyrrolidone. It is provided by coating the surface of the substrate together with the hydrophilic polymer. A paper provided with such an ink receiving layer is usually called an ink jet exclusive paper (film) or glossy paper (film). For example, Pictorico (trade name, manufactured by Asahi Glass Co., Ltd.), color BJ paper, color BJ photo film sheet (All are trade names, manufactured by Canon), Color Image Jet Paper (trade names, manufactured by Sharp), Glossy Film for Super Fine (trade names, manufactured by Seiko Epson), Picta Fine (trade names, manufactured by Hitachi Maxell), etc. Is commercially available. Of course, plain paper without such a receiving layer can also be used.

  As for the fibers, cellulose fibers or polyamide fibers such as nylon, silk and wool are preferable, and non-woven fabrics and cloth-like ones are preferable. For these fibers, after applying the ink composition of the present invention to the fibers, preferably by an inkjet method, wet heat (for example, about 80 to 120 ° C.) or dry heat (for example, about 150 to 180 ° C.) By adding a fixing step, the inside of the fiber can be dyed, and a dyed product excellent in sharpness, light resistance and washing resistance can be obtained.

  The container of the present invention contains the above-described aqueous magenta ink composition. Further, the ink jet printer of the present invention is one in which the container of the present invention containing this aqueous magenta ink composition is set in the ink tank portion. Furthermore, the colored product of the present invention is prepared by using the novel anthrapyridone compound represented by the above formula (1) or a salt thereof as it is or as a composition containing additives as necessary. It is obtained by coloring by a method such as coating, printing, or impregnation, and is preferably colored by the above-mentioned aqueous magenta ink composition.

  The water-based ink composition of the present invention is clear and has an ideal magenta color, and can provide a recorded material that is particularly excellent in ozone resistance and light resistance, moisture resistance, and water resistance. By using with other yellow and cyan inks, it is possible to produce a color tone in a wide visible range, and it is used with existing yellow, cyan and black that are excellent in ozone resistance, light resistance, moisture resistance and water resistance. Thus, a recorded matter excellent in ozone resistance, light resistance, moisture 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 mass unless otherwise specified.

Example 1
(1) Into 360 parts of xylene, 94.8 parts of the compound of the formula (7) (R ₁ = CH ₃ ), 3.0 parts of sodium carbonate, and 144.0 parts of benzoylacetic acid ethyl ester were sequentially added while stirring. The temperature rose. The reaction was carried out at a temperature of 140 to 150 ° C. for 8 hours, during which ethanol and water produced by the reaction were distilled out of the system while azeotroping with xylene to complete the reaction. Subsequently, the reaction mixture was cooled, 240 parts of methanol was added at 30 ° C., stirred for 30 minutes, filtered, washed with 360 parts of methanol, dried, and then compound 124. of formula (8) (R ₁ = CH ₃ ). 8 parts were obtained as pale yellow needles.
(2) Next, while stirring, in 300.0 parts of N, N-dimethylformamide, 88.8 parts of the compound of formula (8) (R ₁ = CH ₃ ), 75.0 parts of metaaminoacetanilide, acetic acid 24.0 parts of copper monohydrate and 12.8 parts of sodium carbonate were sequentially added, and the temperature was raised. The reaction is carried out at 120 to 130 ° C. for 3 hours. Under cooling to about 50 ° C., 120 parts of methanol was added, stirred for 30 minutes, filtered, washed with 500 parts of methanol, then washed with hot water at 80 ° C. and dried to obtain the formula (9) (R ₁ = CH ₃ ) Was obtained as bluish red crystals.

(3) Next, 170.0 parts of 28.0% fuming sulfuric acid were added to 130 parts of 98.0% sulfuric acid while stirring and cooling with water to prepare 300 parts of 12% fuming sulfuric acid. Under water cooling, 51.3 parts of the compound of formula (9) (R ₁ = CH ₃ ) was added at 50 ° C. or lower, the temperature was raised, and the reaction was carried out at 85 to 90 ° C. for 4 hours. Next, the sulfonation reaction solution obtained above was added to 600 parts of ice water, and kept at 50 ° C. or lower while adding ice. Water was added to bring the liquid volume to 1000 parts, followed by filtration to remove insoluble matters. Next, hot water was added to the mother liquor to make 1500 parts, and while maintaining the temperature at 60 to 65 ° C., 300 parts of sodium chloride was added and stirred for 3 hours, and the precipitated crystals were filtered. Wash with 300 parts of a 20% saline solution and carefully squeeze 100.3 parts of wet cake containing 59.2 parts of the compound of formula (3) (R ₁ = CH ₃ ) (purity 45.9% (by diazo analysis). The same applies hereinafter))) as red crystals.

(4) Add 67.7 parts of a wet cake (purity 45.9%) of the compound of formula (3) obtained in (3) above in 60 parts of water, then add 24 parts of 25% caustic soda and stir. Further, 25% caustic soda was added to dissolve the solution while adjusting the pH to 3-4.
On the other hand, 0.4 parts of Lipar OH (trade name, anionic surfactant, manufactured by Lion Corporation) was added to 60 parts of ice water, 8.9 parts of cyanuric chloride was added after dissolution, and the resulting mixture was stirred for 30 minutes. The suspension is added to the solution containing the above formula (3), and the primary condensation is performed at 25 to 30 ° C. for 3 hours while keeping PH at 2.7 to 3.0 while dropping a 10% aqueous sodium hydroxide solution. the reaction was carried out to obtain a reaction solution containing the compound of formula _{(4) (R 1 = CH} 3).
(5) In the reaction solution containing the compound of the formula (4) (R ₁ = CH ₃ ) obtained in the above (4), 8.4 parts of alternic acid (purity 98.89%), 40 parts of water, A solution consisting of 8 parts of a 25% aqueous sodium hydroxide solution was added, and water was further added to bring the liquid volume to 300 parts. While a 10% aqueous sodium hydroxide solution was added dropwise at a temperature of 60 to 70 ° C., the pH was kept at 6.0 to 6.5, and the reaction was allowed to proceed for 1 hour to carry out a secondary condensation reaction. Formula (5) (R ₁ = CH ₃ , X = 2-sulfoanilino group) was obtained.
(6) While adding a 25% aqueous sodium hydroxide solution to the reaction solution containing the compound of the formula (5) (R ₁ = CH ₃ , X = 2-sulfoanilino group) obtained in (5) above, the pH is adjusted to 10. While maintaining the temperature at 0 to 10.2, the reaction was performed at a temperature of 85 to 90 ° C for 1 hour. After the reaction, water was added to adjust the liquid volume to 400 parts, followed by filtration to remove insoluble matters.
Water was added to the resulting reaction liquid to adjust the liquid volume to 500 parts. While maintaining the temperature at 50 to 55 ° C., 100 parts of sodium chloride was added, and then concentrated hydrochloric acid was added to adjust the pH to 0.5, followed by stirring for 1 hour, filtering off the crystals, and 200 parts of a 20% saline solution. To give 92 parts of a compound of formula (6) (R ₁ = CH ₃ , X = 2-sulfoanilino group, Y = OH) as a red wet cake.
(7) The wet cake obtained in (6) above was added to 200 parts of methanol, heated and dissolved at 60 to 65 ° C., and then kept at about 5 ° C. for 1 hour under ice-cooling and then precipitated. The crystals were filtered, washed with methanol, and dried to obtain 25.6 parts of a compound of the following formula (10) (No. 32 compound in Table 1) as red crystals.
λmax: 545.0 nm (in aqueous solution)

Example 2
(1) After adding 0.4 parts of Lipar OH to 100 parts of ice water and dissolving, 8.9 parts of cyanuric chloride is added and stirred for 30 minutes, and 2,5-disulfoaniline (AS acid is added to the resulting suspension. ) 13.2 parts (purity 91.7%) was added, and the reaction was carried out at 15 to 20 ° C. while maintaining the pH at 2.7 to 3.3 while dropping a 25% aqueous sodium hydroxide solution to obtain a primary condensation reaction solution. It was. Next, 67.7 parts of the wet cake (purity 45.9%) of the compound of the formula (3) obtained in (3) of Example 1 is added, and then 24 parts of 25% caustic soda is added to adjust the pH. While maintaining at 5-6, the mixture is stirred at 60-70 ° C. for 4 hours to carry out a secondary condensation reaction, and contains a compound of the formula (5) (R ₁ = CH ₃ , X = 2,5-disulfoanilino group) A liquid was obtained.
(2) A 25% caustic soda aqueous solution was added to the reaction solution of (1) above, and the reaction was carried out at a temperature of 90 to 95 ° C. for 1 hour while adjusting the pH to 10.8 to 11.2. After the reaction, water is added to adjust the liquid volume to 400 parts, and the insoluble matter is removed by filtration. Water was added to the obtained reaction liquid to adjust the liquid volume to 500 parts, 100 parts of sodium chloride was added while heating and maintaining at 60 to 65 ° C., and then hydrochloric acid was added to adjust PH to 0.5. Then, it stirred for 30 minutes. The obtained crystals were filtered off and washed with 200 parts of a 20% aqueous sodium chloride solution to obtain a compound of formula (6) (R ₁ = CH ₃ , X = 2,5-disulfoanilino group, Y = OH) as a bright red wet cake As a result, 73 parts were obtained.
(3) The wet cake obtained in the above (2) is added to 500 parts of methanol and stirred at 20 to 25 ° C. for 1 hour, and then the crystals are filtered, washed with methanol, dried and dried by the following formula (11) (Table 31.3 parts of compound No. 1 in No. 1) was obtained as red crystals.
λmax: 543.0 nm (in aqueous solution)

Example 3
(A) Preparation of ink An ink composition having the composition shown in the following Table 2 containing the anthrapyridone compound (pigment component) of the present invention obtained in each of Examples 1 and 2 was prepared, and a 0.45 μm membrane filter was used. By filtering, each water-based magenta ink composition for inkjet was obtained.
Water used was ion exchange water. Water and ammonium hydroxide were added so that the pH of the ink composition was pH = 8 to 10 and the total amount was 100 parts.

Table 2
5.0 parts of each pigment obtained in Example 1 or Example 2 (use desalted one)
Water + ammonium hydroxide 75.9 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts IPA (isopropyl alcohol) 3.0 parts Butyl carbitol 2.0 parts Surfactant ( Surfinol 104PG50 Nissin Chemical Co., Ltd.)
0.1 part total 100.0 part

(B) Inkjet printing Using an inkjet printer (trade name Canon BJ S-630), plain paper, professional photo paper (PR-101 (made by Canon)), photo glossy film (HG-201 (made by Canon)) ), Four types of recording materials of PM photographic paper <Glossy> (manufactured by Seiko Epson) were subjected to ink jet recording.
(The abbreviations used below mean PR = Professional Photo Paper, HG = Photo Glossy Film, PM = PM Photo Paper <Glossy>, respectively)
At the time of printing, an image pattern was created and printed so that gradations with several levels of reflection density were obtained. In the test described below, the measurement was performed using the gradation portion where the reflection density D value of the printed material before the test was closest to 1.0.

(C) Evaluation of recorded image (1) Hue evaluation Hue and sharpness of recorded image: L ^* , a ^* , and b ^* values were measured using a color measurement system (Gretag Macbeth SpectroEye: GRETAG) for recording paper. did. The sharpness was calculated by C ^* = ((a ^* ) ² + (b ^* ) ² ) ^1/2 . The results are shown in Table 3.
(2) Light resistance test A recorded image was irradiated for 50 hours at 24 ° C. and 60% RH using a xenon weather meter (manufactured by Atlas). The density (D value) before and after irradiation was measured using the above colorimetric system, and the residual ratio was calculated by the following formula.
Residual rate (%) = D value after irradiation / D value before irradiation is shown in Table 3.
(3) Ozone resistance test The test piece printed on the recorded image is left at 24 ° C., 12 ppm, 60% RH for 2 hours using an ozone weather meter (Model OMS-H manufactured by Suga Test Instruments Co., Ltd.). D value) was measured, and the residual ratio was calculated by the following formula.
Residual rate (%) = D value after treatment / D value before treatment is shown in Table 3.

  Table 3 shows the test results of hue, sharpness, light resistance and ozone resistance of the recorded image. The results of evaluating the ink composition prepared using the compound obtained in Example 1 were evaluated in Example 1, and the result of evaluating the ink composition prepared using the compound obtained in Example 2 in the same manner. Is referred to as Evaluation Example 2. As Comparative Example 1, the results of evaluation using the anthrapyridone compound (No. 4 compound) of Example 2 of Patent Document 3 are also shown in Table 3.

Table 3
Hue Sharpness Light resistance Ozone resistance
L ^* a ^* b ^* C ^* (Remaining rate%) (Residual rate%)
Evaluation Example 1
Plain paper 47.7 60.4 -17.1 62.8 96 99
PR 56.7 70.2 -33.3 77.7 96 91
HG 57.1 70.8 -33.5 78.3 96 89
PM 58.0 70.2 -34.2 78.1 97 96

Evaluation example 2
Plain paper 50.1 62.8 -15.7 64.7 96 99
PR 57.8 72.5 -31.7 79.1 89 97
HG 58.4 71.1 -31.1 77.7 86 98
PM 59.5 72.5 -33.2 79.4 95 99

Comparative Example 1
Plain paper 52.6 57.6-0.6 57.6 96 99
PR 59.0 69.2 -14.0 70.6 85 51
HG 58.8 68.9 -15.8 70.7 83 61
PM 60.6 68.1 -14.8 69.7 89 65

From Table 3, the C ^* values of Evaluation Examples 1 and 2 are higher than those of Comparative Example 1, and the sharpness is higher. Further, the ozone resistance of Evaluation Examples 1 and 2 has a higher residual ratio than that of Comparative Example 1, indicating that the image stability by ozone gas or the like is surprisingly improved. Furthermore, the light resistance of Evaluation Examples 1 and 2 is higher than that of Comparative Example 1, indicating that the anthrapyridone compound of the present invention is an excellent compound as a magenta dye for inkjet.

Example 4
(1) 24 parts of concentrated aqueous ammonia (28%) was added to the reaction solution containing the compound of the formula (5) (R ₁ = CH ₃ , X = 2-sulfoanilino group) obtained in (5) of Example 1. In addition, the mixture was heated to 90 ° C. and reacted for 30 minutes. After the reaction, filtration was performed to remove insoluble matters. Water was added to the resulting reaction solution to adjust the liquid volume to 800 parts. While maintaining the temperature at 50 to 60 ° C., 160 parts of sodium chloride was added, and then concentrated hydrochloric acid was added to adjust the pH to 0, followed by stirring for 30 minutes. The crystals were separated by filtration and washed with 400 parts of 20% aqueous sodium chloride solution. As a result, 100 parts of a compound of the formula (6) (R ₁ = CH ₃ , X = 2-sulfoanilino group, Y = NH ₂ ) was obtained as a red wet cake.
(2) The wet cake obtained in (1) above is added to 800 parts of methanol, heated to 60 to 65 ° C., stirred, filtered, washed with methanol, and dried, then the following formula (12) (No in Table 1) Compound 2) was obtained as red crystals.
λmax: 544.8 nm (in aqueous solution)

Example 5
(1) 10.2 parts of 4-methoxy-2-sulfoaniline (purity 99) in the reaction solution containing the compound of formula (4) (R ₁ = CH ₃ ) obtained in (4) of Example 1 0.4%), 40 parts of water, and 7.8 parts of 25% aqueous sodium hydroxide solution were added, and water was added to bring the liquid volume to 300 parts. While adding a 25% aqueous solution of sodium hydroxide at 60 to 70 ° C., the pH is kept at 5.0 to 6.0, the reaction is carried out for 30 minutes, and the secondary condensation reaction is carried out, and the formula (5) (R ₁ = CH ₃ , A reaction solution containing a compound of X = 4-methoxy-2-sulfoanilino group) was obtained.
(2) A 25% aqueous solution of sodium hydroxide is added to the reaction solution containing the compound of the formula (5) (R ₁ = CH ₃ , X = 4-methoxy-2-sulfoanilino group) obtained in (1) above to adjust the pH to 10 The mixture was reacted at 90 ° C. for 1 hour while maintaining the temperature at 0.0-10.2. After the reaction, filtration was performed to remove insoluble matters. Water was added to the obtained filtrate to adjust the liquid volume to 1200 parts. At room temperature (about 20 ° C.), 240 parts of sodium chloride was added, then concentrated hydrochloric acid was added to adjust the pH to 0, and the mixture was stirred for 30 minutes. The crystals were separated by filtration, washed with 400 parts of a 20% saline solution, and washed. (6) 100 parts of a compound of (R ₁ = CH ₃ , X = 4-methoxy-2-sulfoanilino group, Y = OH) was obtained as a red wet cake.
(3) The wet cake obtained in the above (2) is added to 800 parts of methanol, stirred at room temperature (about 20 ° C.) for 1 hour, filtered, washed with methanol and dried, then the following formula (13) (Table 20.4 parts of compound No. 36 in No. 1) was obtained as red crystals.
λmax: 541.4 nm (in aqueous solution)

Example 6
(1) In a reaction solution containing the compound of the formula (4) (R ₁ = CH ₃ ) obtained in (4) of Example 1, 15.0 parts of 4-sulfoanthranilic acid (purity 76.4%) ), 60 parts of water and 16.8 parts of 25% aqueous sodium hydroxide solution were added, and water was further added to bring the liquid volume to 400 parts, and the temperature was raised. While dropping a 25% aqueous solution of sodium hydroxide at 50 to 60 ° C., the pH is kept at 4.5 to 5.0, the reaction is carried out for 30 minutes, and the secondary condensation reaction is carried out, and the formula (5) (R ₁ = CH ₃ , A reaction solution containing a compound of X = 2-carboxy-5-sulfoanilino group) was obtained.
(2) A 25% aqueous sodium hydroxide solution is added to the reaction solution containing the compound of formula (5) (R ₁ = CH ₃ , X = 2-carboxy-5-sulfoanilino group) obtained in (1) above to adjust the pH. The mixture was reacted at 85 to 90 ° C. for 1 hour while maintaining 10.0, and further reacted at 85 to 90 for 1 hour while maintaining the pH at 11.0. After the reaction, filtration was performed to remove insoluble matters. Water was added to the obtained filtrate to adjust the liquid volume to 600 parts. While maintaining the temperature at 30 to 35 ° C., 120 parts of sodium chloride was added, and then concentrated hydrochloric acid was added to adjust the pH to 0.5, followed by stirring for 1 hour, the crystals were filtered off, and 60 parts of 20% saline solution was added. Washing gave 100 parts of the compound of formula (6) (R ₁ = CH ₃ , X = 2-carboxy-5-sulfoanilino group, Y = OH) as a red wet cake.
(3) The wet cake obtained in the above (2) is added to 600 parts of methanol and 40 parts of water, stirred at 60 to 65 ° C. for 30 minutes, filtered, washed with methanol and dried, then the following formula (14) 16.6 parts of compound (No. 38 compound in Table 1) were obtained as red crystals.
λmax: 540.0 nm (in aqueous solution)

Example 7
(1) 7.9 parts of 3-carboxy-4-hydroxyaniline (purity 98) in the reaction solution containing the compound of the formula (4) (R ₁ = CH ₃ ) obtained in (4) of Example 1 %), 40 parts of water, and 8 parts of a 25% aqueous solution of caustic soda, and water was added to bring the liquid volume to 400 parts, and the temperature was raised. While dropping a 25% aqueous sodium hydroxide solution at 50 to 60 ° C., the pH is kept at 4.5 to 5.0, the reaction is carried out for 2 hours, and the secondary condensation reaction is carried out, and the formula (5) (R ₁ = CH ₃ , X = 3-carboxy-4-hydroxyanilino group) was obtained.
(2) A 25% aqueous sodium hydroxide solution was added to the reaction solution containing the compound of formula (5) (R ₁ = CH ₃ , X = 3-carboxy-4-hydroxyanilino group) obtained in (1) above. The reaction was carried out at 85 to 90 ° C. for 2 hours while maintaining the pH at 10.8 to 11.0. After the reaction, filtration was performed to remove insoluble matters. Water was added to the obtained filtrate to adjust the liquid volume to 600 parts. While maintaining the temperature at 60 to 65 ° C., 60 parts of sodium chloride was added, then concentrated hydrochloric acid was added to adjust the pH to 2.0, and the mixture was stirred for 30 minutes, and the crystals were separated by filtration. Washing gave 88 parts of the compound of formula (6) (R ₁ = CH ₃ , X = 3-carboxy-4-hydroxyanilino group, Y = OH) as a red wet cake.
(3) The wet cake obtained in the above (2) is added to 800 parts of methanol, heated to 65 ° C., stirred for 30 minutes, filtered, washed with methanol, and dried to obtain the following formula (15) (Table 1). 33.6 parts of compound No. 41 in No. 41) was obtained as red crystals.
λmax: 539.0 nm (in aqueous solution)

Example 8
Inks were prepared in the same manner as in Example 3 (A) to (C), ink jet print recording, and then image evaluation. However, for the printing paper, inkjet recording was performed on three types of recording materials: plain paper, professional photo paper (PR-101 (manufactured by Canon Inc.)), and super photo paper (SP-101 (manufactured by Canon Inc.)).
(The abbreviations used below mean PR = Professional Photo Paper and SP = Super Photo Paper, respectively)
Table 4 shows the test results of hue, sharpness, light resistance and ozone resistance of the recorded image. The results of evaluating the ink composition prepared using the compound obtained in Example 4 were evaluated in Evaluation Example 3, and the results of evaluating the ink composition prepared using the compound obtained in Example 5 were evaluated. 4. Evaluation results of ink compositions prepared using the compounds obtained in Example 6 were evaluated in Evaluation Example 5, and ink compositions prepared using the compounds obtained in Example 7 were evaluated. Is referred to as Evaluation Example 6.

Table 4
Hue Sharpness Light resistance Ozone resistance
L ^* a ^* b ^* C ^* (Remaining rate%) (Residual rate%)
Evaluation Example 3
Plain paper 47.0 58.7 -19.9 62.0 97 99
PR 46.4 72.3 -32.3 79.2 81 92
SP 55.6 71.3 -31.2 77.8 94 94

Evaluation Example 4
Plain paper 49.3 59.8 -14.4 61.5 95 99
PR 49.7 69.0 -26.3 73.8 85 90
SP 58.9 68.3 -25.8 73.0 92 91

Evaluation Example 5
Plain paper 47.6 55.0 -19.1 58.2 96 99
PR 50.0 65.6 -33.1 73.5 90 95
SP 57.1 65.0 -30.6 71.8 94 96

Evaluation Example 6
Plain paper 47.8 55.8 -16.0 58.0 98 99
PR 57.7 67.3 -27.2 72.6 93 93
SP 57.7 67.2 -28.4 73.0 96 93

From Table 4, the C ^* values of Evaluation Examples 3 to 6 are high and the sharpness is high. Moreover, the light resistance and ozone resistance of Evaluation Examples 3 to 6 are extremely high, and it can be seen that the anthrapyridone compound of the present invention is an excellent compound as a magenta dye for inkjet.

  The anthrapyridone compound of the present invention is comprehensively superior to the compound of the comparative example, and shows stable and high quality on each medium (recording material). Furthermore, the pigments obtained in Examples 1 to 3 each have a solubility in water of 100 g / l or more under alkaline conditions (pH = 8 to 9), and it is possible to prepare a stable ink as a pigment for inkjet. In addition, since it is possible to prepare a high-concentration ink, it is a compound that can be used in a wide range of applications.

Claims (13)

Formula (1)

(In the formula (1), R ₁ represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a mono- or dialkylaminoalkyl group or a cyano lower alkyl group, and X represents a sulfonic acid group, a methoxy group, an anilino group, or a phenoxy group. An anilino group optionally substituted with a group; a methyl-sulfoanilino group; a methoxy-sulfoanilino group; a carboxy-sulfoanilino group; a carboxy-hydroxyanilino group; a naphthylamino group optionally substituted with a sulfonic acid group; , Carboxy group, mono or dialkylamino group optionally substituted with hydroxyl group; aralkylamino group; cycloalkylamino group; substituted with sulfonic acid group, carboxyl group, acetylamino group, amino group, hydroxyl group, phenoxy group or phenyl group Fenoki which may have been Group: monoalkylaminoalkylamino group; dialkylaminoalkylamino group; hydroxyl group or amino group, Y is chlorine atom, hydroxyl group, amino group, mono- or dialkylamino group (from sulfonic acid group, carboxy group and hydroxyl group on the alkyl group) Each may have a substituent selected from the group consisting of: or a morpholino group)
An anthrapyridone compound or a salt thereof The anthrapyridone compound or a salt thereof according to claim 1, wherein R ₁ in the formula (1) is a methyl group. The anthrapyridone compound or a salt thereof according to claim 1 or 2, wherein Y in formula (1) is a hydroxyl group or an amino group. X in the formula (1) is an anilino group, 2-sulfoanilino group, 2,5-disulfoanilino group, 2-ethylhexylamino group or cyclohexylamino group, 4-methoxy-2-sulfoanilino group, 2-carboxy-5-sulfoanilino group. An anthrapyridone compound or a salt thereof according to any one of claims 1 to 3, which is a 3-carboxy-4-hydroxyanilino group. An aqueous magenta ink composition comprising the anthrapyridone compound or a salt thereof according to any one of claims 1 to 4 as a dye component. The aqueous magenta ink composition according to claim 5, comprising a water-soluble organic solvent. The aqueous magenta ink composition according to claim 5 or 6, wherein the content of the inorganic salt in the anthrapyridone compound or a salt thereof is 1% by mass or less. The aqueous magenta ink composition according to any one of claims 5 to 7, which is for ink jet recording. In an ink jet recording method in which ink droplets are ejected according to a recording signal and recording is performed on a recording material, the aqueous magenta ink composition according to any one of claims 5 to 7 is used as ink. Inkjet recording method 10. The ink jet recording method according to claim 9, wherein the recording material is an information transmission sheet. A container containing the aqueous magenta ink composition according to any one of claims 5 to 7. An ink jet printer having the container of claim 11. The colored body which has an anthrapyridone compound as described in any one of Claim 1 to 4, or its salt.