JPWO2010084740A1 - Anthrapyridone compound or salt thereof, magenta ink composition, and colored product - Google Patents

Abstract

Magenta dye (anthrapyridone compound or salt thereof) having high solubility in water, hue and sharpness suitable for ink jet recording, and excellent balance of fastness such as light resistance and gas resistance of recorded matter, and the like An ink composition is provided. The anthrapyridone compound is represented by the following formula (1). In the formula, X represents a heteroaromatic ring, n represents an integer of 1 to 3, R1 represents a hydrogen atom, R2 represents a hydrogen atom, an alkyl group, or the like, and R3 is substituted with a carboxyl group. Represents an alkylamino group or the like, and a to d represent the substitution positions of two sulfo groups whose substitution positions are not specified.

Description

  The present invention relates to a novel anthrapyridone compound or a salt thereof, a magenta ink composition containing an anthrapyridone compound or a salt thereof, and a colored body colored with this composition or the like.

Among various color recording methods, various ink ejection methods have been developed in an inkjet recording method which is one of the representative methods. In any of these recording methods, ink droplets are generated and recorded on various recording materials (paper, film, fabric, etc.). In this method, since the recording head and the recording material do not come into contact with each other, no noise is generated and the method is quiet. In addition, since it has the features that it is easy to downsize, speed up, and colorize, it has been spreading rapidly in recent years and is expected to grow greatly in the future.
Conventionally, water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used as inks such as fountain pens and felt-tip pens and inks for inkjet recording. In these water-based inks, a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle. With these conventional inks, it is possible to provide a recording image with sufficient density, no clogging of the pen tip and nozzles, good drying on the recording material, less bleeding, and storage stability. It is required to be excellent. Various fastnesses are required for the formed image.

  On the other hand, 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 color inks of yellow (Y), magenta (M), cyan (C), and black (K) are used. Expressed in subtractive color mixing. To reproduce an additive color mixture image of red (R), green (G), and blue (B) such as a CRT display as faithfully as possible with a subtractive color mixture image, each of Y, M, and C can be set as a standard. It is desirable to have a hue close to each other and to be clear. In addition, 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 various fastness properties.

Applications of inkjet printers have been expanded from OA small printers to industrial large printers, and it is excellent in various fastnesses such as water resistance, moisture resistance, light resistance, gas resistance, and the balance thereof. More than is required.
Water resistance has been greatly improved by coating the surface of the recording material with inorganic fine particles capable of adsorbing pigments in inks such as porous silica, cationic polymers, alumina sol, and special ceramics together with PVA resin. ing.
Moisture resistance refers to resistance to a phenomenon in which a dye in a recording material oozes when the colored recording material is stored in a high humidity atmosphere. If there is a blur of the dye, the image quality is remarkably deteriorated particularly in an image that requires a high-definition image quality such as a photographic tone. Therefore, it is important to reduce such a blur as much as possible.
Regarding the light resistance, a technology for significantly improving the light resistance has not yet been established, and in particular, among the four primary colors Y, M, C, and K, many of the magenta dyes have inherently low light resistance, and the improvement is an important issue. It has become.
In addition, with the recent penetration of digital cameras, there are increasing opportunities for inkjet recording with photographic image quality even at home, and the deterioration of images due to oxidizing gas in the air when storing the obtained recorded matter is also a problem. Has been. This oxidizing gas reacts with the dye on the recording material or in the recording material, and changes the color of the recorded image. Among oxidizing gases, ozone gas is regarded as a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Since this discoloration phenomenon is characteristic of ink jet images, improvement of ozone gas resistance is also an important issue.

  Typical examples of magenta dyes used in water-based inks for ink jet recording are xanthene dyes and azo dyes using H acid. However, xanthene dyes are very excellent in hue and sharpness but very inferior in light resistance. On the other hand, some azo dyes using H acid are good in terms of hue and water resistance, but are inferior in light resistance, gas resistance, and sharpness. As azo dyes, those with excellent sharpness and light resistance have been developed, but the light resistance is still inferior to other hue dyes such as cyan dyes and yellow dyes typified by copper phthalocyanine dyes. It is.

  Examples of magenta dyes that are excellent in sharpness and light resistance include anthrapyridone dyes (see, for example, Patent Documents 1 to 13), and all of hue, sharpness, light resistance, water resistance, gas resistance, and solution stability are provided. There is nothing to satisfy.

JP-A-10-306221 (pages 1-3 and 7-18) JP 2000-109464 A (pages 1-2 and 8-12) JP 2000-169776 (pages 1-2, 6-9) JP 2000-191660 A (pages 1-3 and 11-14) JP 2000-256587 A (pages 1-3 and 7-18) JP 2001-72884 A (pages 1-2, 8-11) JP 2001-139836 A (1-2 pages, 7-12 pages) International Publication No. 2004/104108 Pamphlet (20-36 pages) JP 2003-192930 A (pages 1-4 and 15-18) JP 2005-8868 (pages 1-3 and 15-22) JP-A-2005-314514 (pages 1-3 and 15-20) International Publication No. 2006/0775706 Pamphlet International Publication No. 2008/018495 Pamphlet

  The present invention has a magenta dye (compound) that has high solubility in water, has hue and sharpness suitable for ink jet recording, and excellent balance of various fastnesses such as moisture resistance and ozone gas resistance of recorded matter, and the like An object of the present invention is to provide an ink composition.

  As a result of intensive studies, the present inventors have found that an anthrapyridone compound represented by the following formula (1) can solve the above-mentioned problems, and have completed the present invention. .

［式（１）中、
ｎは１から３の整数を表し、
Ｘは複素芳香環を表し、
Ｒ_１は、水素原子、カルボキシ基、スルホ基、フェニル基、非置換Ｃ１−Ｃ６アルキル基、非置換Ｃ１−Ｃ６アルコキシ基、又はヒドロキシ基を表し、
Ｒ_２は、水素原子、非置換Ｃ１−Ｃ１０アルキル基、ヒドロキシＣ１−Ｃ６アルキル基、モノＣ１−Ｃ１０アルキルアミノＣ１−Ｃ１０アルキル基、ジＣ１−Ｃ１０アルキルアミノＣ１−Ｃ１０アルキル基、又はシアノＣ１−Ｃ６アルキル基を表し、
Ｒ_３は、塩素原子；モノ非置換Ｃ１−Ｃ１２アルキルアミノ基；スルホ基、カルボキシ基、アルコキシ基、カルバモイル基、シアノ基、アニリノ基、アミノ基、モノ非置換Ｃ１−Ｃ４アルキルアミノ基、ジ非置換Ｃ１−Ｃ４アルキルアミノ基、フェノキシ基、ヒドロキシ基、フェニル基、及びメルカプト基よりなる群から選択される基で置換されたモノＣ１−Ｃ１２アルキルアミノ基；ジ非置換Ｃ１−１２アルキルアミノ基；スルホ基、カルボキシ基、アルコキシ基、カルバモイル基、シアノ基、アニリノ基、アミノ基、モノ非置換Ｃ１−Ｃ４アルキルアミノ基、ジ非置換Ｃ１−Ｃ４アルキルアミノ基、フェノキシ基、ヒドロキシ基、フェニル基、及びメルカプト基よりなる群から選択される基で置換されたジＣ１−Ｃ１２アルキルアミノ基；非置換アニリノ基；スルホ基、カルボキシ基、非置換Ｃ１−Ｃ４アルキル基、非置換Ｃ１−Ｃ４アルコキシ基、カルバモイル基、シアノ基、アニリノ基、アミノ基、モノ非置換Ｃ１−Ｃ４アルキルアミノ基、ジ非置換Ｃ１−Ｃ４アルキルアミノ基、フェノキシ基、ヒドロキシ基、フェニル基、及びメルカプト基よりなる群から選択される基で置換されたアニリノ基；非置換Ｃ１−Ｃ１０アルキルチオ基；スルホ基、カルボキシ基、非置換Ｃ１−Ｃ４アルコキシ基、カルバモイル基、シアノ基、アニリノ基、アミノ基、モノ非置換Ｃ１−Ｃ４アルキルアミノ基、ジ非置換Ｃ１−Ｃ４アルキルアミノ基、フェノキシ基、ヒドロキシ基、フェニル基、及びメルカプト基よりなる群から選択される基で置換されたＣ１−Ｃ１０アルキルチオ基；非置換フェニルチオ基；スルホ基、カルボキシ基、非置換Ｃ１−Ｃ４アルキル基、非置換Ｃ１−Ｃ４アルコキシ基、カルバモイル基、シアノ基、アニリノ基、アミノ基、フェノキシ基、ヒドロキシ基、フェニル基、及びメルカプト基よりなる群から選択される基で置換されたフェニルチオ基；非置換フェノキシ基；スルホ基、カルボキシ基、非置換Ｃ１−Ｃ４アルキル基、非置換Ｃ１−Ｃ４アルコキシ基、カルバモイル基、シアノ基、アニリノ基、アミノ基、フェノキシ基、ヒドロキシ基、フェニル基、及びメルカプト基よりなる群から選択される基で置換されたフェノキシ基；モノＣ１−Ｃ１０アルキルアミノＣ１−Ｃ１０アルキルアミノ基；又はジＣ１−Ｃ１０アルキルアミノＣ１−Ｃ１０アルキルアミノ基；を表し、
ａ乃至ｄは、置換位置の特定されていない２つのスルホ基の置換位置を表す。］That is, the present invention
1)
An anthrapyridone compound represented by the following formula (1) or a salt thereof,

[In Formula (1),
n represents an integer of 1 to 3,
X represents a heteroaromatic ring,
R ₁ represents a hydrogen atom, a carboxy group, a sulfo group, a phenyl group, an unsubstituted C1-C6 alkyl group, an unsubstituted C1-C6 alkoxy group, or a hydroxy group,
R ₂ is a hydrogen atom, an unsubstituted C1-C10 alkyl group, a hydroxy C1-C6 alkyl group, a mono C1-C10 alkylamino C1-C10 alkyl group, a di-C1-C10 alkylamino C1-C10 alkyl group, or a cyano C1- Represents a C6 alkyl group,
R ₃ represents a chlorine atom; a mono-unsubstituted C1-C12 alkylamino group; a sulfo group, a carboxy group, an alkoxy group, a carbamoyl group, a cyano group, an anilino group, an amino group, a mono-unsubstituted C1-C4 alkylamino group, a di-non group A mono C1-C12 alkylamino group substituted with a group selected from the group consisting of a substituted C1-C4 alkylamino group, a phenoxy group, a hydroxy group, a phenyl group, and a mercapto group; a di-unsubstituted C1-12 alkylamino group; Sulfo group, carboxy group, alkoxy group, carbamoyl group, cyano group, anilino group, amino group, mono-unsubstituted C1-C4 alkylamino group, di-unsubstituted C1-C4 alkylamino group, phenoxy group, hydroxy group, phenyl group, And a diC1-C12 alkylamino group substituted with a group selected from the group consisting of mercapto groups An unsubstituted anilino group; a sulfo group, a carboxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a carbamoyl group, a cyano group, an anilino group, an amino group, a mono-unsubstituted C1-C4 alkylamino group; An anilino group substituted with a group selected from the group consisting of a di-unsubstituted C1-C4 alkylamino group, a phenoxy group, a hydroxy group, a phenyl group, and a mercapto group; an unsubstituted C1-C10 alkylthio group; a sulfo group, a carboxy group Unsubstituted C1-C4 alkoxy group, carbamoyl group, cyano group, anilino group, amino group, mono-unsubstituted C1-C4 alkylamino group, di-unsubstituted C1-C4 alkylamino group, phenoxy group, hydroxy group, phenyl group, And a C1-C10 alkylthio group substituted with a group selected from the group consisting of a mercapto group; Phenylthio group; from sulfo group, carboxy group, unsubstituted C1-C4 alkyl group, unsubstituted C1-C4 alkoxy group, carbamoyl group, cyano group, anilino group, amino group, phenoxy group, hydroxy group, phenyl group, and mercapto group A phenylthio group substituted with a group selected from the group consisting of: an unsubstituted phenoxy group; a sulfo group, a carboxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a carbamoyl group, a cyano group, an anilino group, A phenoxy group substituted with a group selected from the group consisting of an amino group, a phenoxy group, a hydroxy group, a phenyl group, and a mercapto group; a mono C1-C10 alkylamino C1-C10 alkylamino group; or a diC1-C10 alkylamino A C1-C10 alkylamino group;
a to d represent the substitution positions of two sulfo groups whose substitution positions are not specified. ]

2)
The anthrapyridone compound or a salt thereof according to 1) above, wherein the heteroaromatic ring in X is a 5-membered or 6-membered heteroaromatic ring;
3)
The anthrapyridone compound or salt thereof according to 1) or 2) above, wherein the heteroaromatic ring in X is a 5-membered or 6-membered nitrogen-containing heteroaromatic ring containing one or two nitrogen atoms as ring-constituting atoms ,
4)
The anthrapyridone compound or the salt thereof according to any one of 1) to 3) above, wherein X is a pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, furan ring, benzothiazole ring, thiazole ring, or imidazole ring. ,
5)
The anthrapyridone compound or a salt thereof according to any one of 1) to 3) above, wherein X is a pyridine ring, a pyrazine ring, a pyridazine ring, or a pyrimidine ring,
6)
n is 1 or 2,
An anthrapyridone compound or a salt thereof according to any one of 1) to 5) above, wherein R ₂ is a hydrogen atom or an unsubstituted C1-C4 alkyl group,

［式（２）中、ｎ、Ｒ_１乃至Ｒ_３、及びａ乃至ｄは、式（１）におけるのと同じ意味を表す。］7)
The anthrapyridone compound or a salt thereof according to any one of 1) to 6) represented by the following formula (2):

[In the formula (2), n, R _{1 to} R ₃ , and a to d represent the same meaning as in the formula (1). ]

8)
R ₁ is a hydrogen atom, a sulfo group, or unsubstituted a C1-C6 alkyl group, the 1) to 7 anthrapyridone compound or a salt thereof according to any one of)
9)
The anthrapyridone compound or a salt thereof according to any one of 1) to 8) above, wherein R ₁ is a hydrogen atom,
10)
The anthrapyridone compound or a salt thereof according to any one of 1) to 9) above, wherein the substitution positions of two sulfo groups whose substitution positions are not specified are a and c,
11)
R ₃ is a chlorine atom; unsubstituted C1-10 alkylamino group; C1-C10 alkylamino group substituted with sulfo group or carboxy group; unsubstituted C1-10 alkylthio group; substituted with sulfo group, carboxy group, or amino group The anthrapyridone compound or the salt thereof according to any one of 1) to 10) above, which is a substituted C1-10 alkylthio group; a phenylthio group substituted with a carboxy group; or a phenoxy group substituted with a carboxy group; ,
12)
n is 1,
X is a pyridine ring,
R ₁ is a hydrogen atom,
R ₂ is an unsubstituted C1-C4 alkyl group,
R ₃ is a chlorine atom or a C1-C10 alkylamino group substituted with a carboxy group,
The anthrapyridone compound or a salt thereof according to 1) above, wherein the substitution positions of two sulfo groups whose substitution positions are not specified are a and c,
13)
An ink composition containing the anthrapyridone compound or a salt thereof according to any one of 1) to 12) above;
14)
The ink composition according to the above 13), further comprising water and a water-soluble organic solvent;
15)
The content of the inorganic impurity in the compound or the salt thereof is 1 with respect to the total mass of the anthrapyridone compound or the salt thereof according to any one of 1) to 12) contained as a pigment in the ink composition. The ink composition as described in 13) above, which is not more than mass%,
16)
The content of the anthrapyridone compound or a salt thereof according to any one of 1) to 12), which is contained as a pigment in the ink composition, is 0.1 to 20 mass relative to the total mass of the ink composition. %, The ink composition according to the above 13),
17)
The ink composition as described in 13) above, which is for inkjet recording,
18)
An ink jet recording method in which the ink composition according to any one of the above 13) to 17) is used as an ink, and droplets of the ink are ejected in accordance with a recording signal and adhered to a recording material for recording. ,
19)
The inkjet recording method according to 18), wherein the recording material is an information transmission sheet;
20)
The inkjet recording method according to the above 19), wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance,
21)
A colored body colored with the ink composition according to any one of 13) to 17) above,
22)
The colored body according to 21), wherein coloring is performed by an ink jet printer,
23)
An inkjet printer loaded with a container containing the ink composition according to any one of 13) to 17) above;
About.

  The anthrapyridone compound represented by the above formula (1) or a salt thereof according to the present invention has a very clear hue on inkjet recording paper, is excellent in water solubility, and is suitable for a membrane filter in the process of producing an ink composition. It has the characteristic that filterability is favorable. Further, the ink composition of the present invention containing this compound has good storage stability without solid precipitation, physical property change, color change, etc. after long-term storage. The magenta ink composition of the present invention can also faithfully reproduce the hue of a photographic color image on paper. Furthermore, even when recording on a recording material coated with a porous white inorganic material, such as photographic quality inkjet paper (film), the balance of various fastness properties, particularly light resistance and ozone gas resistance, is good. Yes, it has excellent long-term storage stability of photographic-tone recorded images. Therefore, the anthrapyridone compound represented by the above formula (1) or a salt thereof is extremely useful as a magenta dye for ink jet recording.

The present invention will be described in detail. The anthrapyridone compound of the present invention is a water-soluble dye. In the present specification, for the sake of convenience, the term “anthrapyridone compound of the present invention” and the “anthrapyridone compound of the present invention or a salt thereof” are simply described.
In the present specification, unless otherwise specified, acidic functional groups such as a sulfo group and a carboxy group are also expressed in the form of a free acid for convenience, including their salts.

  The compound of the present invention is represented by the above formula (1).

  In the above formula (1), n represents an integer of 1 to 3. n is preferably 1 or 2, and more preferably 1.

In the above formula (1), X represents a heteroaromatic ring. Examples of the heteroaromatic ring include 5-membered or 6-membered heteroaromatic rings.
In addition, the heteroaromatic ring may be a bicyclic structure by condensing one benzene ring, but is preferably a single ring that is not condensed.
Specific examples of heteroaromatic rings include 5-membered nitrogen-containing heteroaromatic rings containing one nitrogen atom such as pyrrole; 5-membered nitrogen-containing heteroaromatic rings containing two nitrogen atoms such as pyrazole and imidazole; nitrogen atoms such as pyridine 6-membered nitrogen-containing heteroaromatic ring containing 1 nitrogen; 6-membered nitrogen-containing heteroaromatic ring containing 2 nitrogen atoms such as pyrazine, pyridazine, pyrimidine, etc .; Oxygen-containing heteroaromatic ring containing 1 oxygen atom such as furan; Or a heteroaromatic ring containing two or more heteroatoms of the above; a monocyclic heteroaromatic ring such as benzothiazole having one benzene ring condensed; and the like.
Among the above heteroaromatic rings, a 5-membered or 6-membered nitrogen-containing heteroaromatic ring containing 1 or 2 nitrogen atoms as ring-constituting atoms is preferred, and a 6-membered ring containing 1 or 2 nitrogen atoms is preferred. A nitrogen-containing heteroaromatic ring is more preferable, and a 6-membered nitrogen-containing heteroaromatic ring containing one nitrogen atom is more preferable.
Specifically, pyridine, pyrazine, pyridazine, pyrimidine, furan, benzothiazole, thiazole and imidazole are preferable, pyridine, pyrazine, pyridazine and pyrimidine are more preferable, and pyridine is particularly preferable.
X has one bond to R ₁ and the adjacent carbonyl, but these bonds have a carbon atom in X, and never have a hetero atom.

In the above formula (1), as the unsubstituted C1-C6 alkyl group for R _1, it can be mentioned a straight or branched, linear is preferred. As carbon number, it is C1-C6 normally, Preferably it is C1-C4. Specific examples include straight chain such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl; branched chain such as isopropyl, isobutyl, 2-methylbutyl and t-butyl; etc. Is mentioned.

Examples of the unsubstituted C1-C6 alkoxy group for R ₁ include straight-chain or branched-chain groups, and straight-chain is preferable. As carbon number, it is C1-C6 normally, Preferably it is C1-C4. Specific examples include straight chain such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy; branched chain such as isopropoxy, isobutoxy, t-butoxy, etc. It is done.

R ₁ is preferably a hydrogen atom, a sulfo group, or an unsubstituted C1-C6 alkyl group, and particularly preferably a hydrogen atom.

In the above formula (1), examples of the unsubstituted C1-C10 alkyl group for R ₂ include linear, branched, or cyclic groups, preferably linear or branched, more preferably linear. is there. As carbon number, it is C1-C10 normally, Preferably it is C1-C6, More preferably, it is C1-C4. Specific examples include straight chain such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; isopropyl, isobutyl , Sec-butyl, t-butyl, isopentyl and the like branched chain; cyclopropyl, cyclohexyl and the like; and the like.

Examples of the hydroxy C1-C6 alkyl group for R ₂ include those in which the alkyl moiety is linear or branched, and linear is preferred. The number of carbon atoms is usually C1-C6, preferably C2-C4. Specific examples thereof include linear ones such as 2-hydroxyethyl, 3-hydroxypropyl and 4-hydroxybutyl; branched ones such as 2-hydroxy-1,2-dimethylethyl;

Examples of the mono C1-C10 alkylamino C1-C10 alkyl group for R ₂ include straight-chain or branched-chain groups, and straight-chain is preferable. The number of carbon atoms is usually a mono C1-C10 alkylamino C1-C10 alkyl group, preferably a mono C1-C6 alkylamino C1-C6 alkyl group, more preferably a mono C1-C4 alkylamino C1-C4 alkyl group. Specific examples include methylaminopropyl and ethylaminopropyl.

Examples of the di-C1-C10 alkylamino C1-C10 alkyl group for R ₂ include straight-chain or branched-chain groups, and straight-chain is preferable. The number of carbon atoms is usually a diC1-C10 alkylamino C1-C10 alkyl group, preferably a diC1-C6 alkylamino C1-C6 alkyl group, more preferably a diC1-C4 alkylamino C1-C4 alkyl group. Specific examples include dimethylaminopropyl and diethylaminoethyl.

Examples of the cyano C1-C6 alkyl group for R ₂ include straight-chain or branched-chain groups, and straight-chain is preferable. As carbon number, it is C1-C6 normally, Preferably it is C1-C4. Specific examples include cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, cyanohexyl and the like.

Among the above, R ₂ is preferably a hydrogen atom or an unsubstituted C1-C4 alkyl group, more preferably an unsubstituted C1-C4 alkyl group, and particularly preferably a methyl group.

In the above formula (1), examples of the mono-unsubstituted C1-C12 alkylamino group in R ₃ include those in which the alkyl portion is linear, branched or cyclic, preferably linear or branched, and more Preferably it is a straight chain. As carbon number, it is C1-C12 normally, Preferably it is C1-C8, More preferably, it is C1-C6. Specific examples include methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, n -Straight chain such as undecylamino, n-dodecylamino; branched chain such as isopropylamino, isobutylamino, sec-butylamino, t-butylamino, isopentylamino, isohexylamino; cyclopropylamino, Cyclic groups such as cyclopentylamino and cyclohexylamino; and the like.

Sulfo group in R _3, a carboxy group, an alkoxy group, a carbamoyl group, a cyano group, an anilino group, an amino group, mono-unsubstituted C1-C4 alkyl group, di unsubstituted C1-C4 alkyl amino group, a phenoxy group, hydroxy group, As the mono C1-C12 alkylamino group substituted with a group selected from the group consisting of a phenyl group and a mercapto group, the alkyl part of the mono-unsubstituted C1-C12 alkylamino group is the above-mentioned substituent. One to three, preferably one or two, more preferably one is substituted. Examples of the alkyl moiety include straight chain or branched chain, and straight chain is preferable. Moreover, carbon number of an alkyl part is C1-C12 normally, Preferably it is C1-C8, More preferably, it is C1-C6.
Specific examples include sulfo-substituted ones such as 2-sulfoethylamino and 3-sulfopropylamino; carboxymethylamino, 2-carboxyethylamino, 4-carboxybutylamino, 5-carboxypentylamino, and 6-carboxyhexylamino. Carboxy-substituted ones such as 2-methoxyethylamino; carbamoyl-substituted ones such as 2-aminocarbonylethylamino; cyano-substituted ones such as 2-cyanoethylamino; 2-phenylaminoethylamino and the like Anilino-substituted ones; amino-substituted ones such as aminoethylamino; mono-unsubstituted C1-C4 alkylamino-substituted ones such as N-methylaminoethylamino; di-unsubstituted C1 such as N, N-dimethylaminoethylamino -C4 alkylamino substituted; Ones phenoxy substituted such as carboxyethyl amino; 2-hydroxyethyl those hydroxy-substituted amino and the like; those phenyl substituted such as benzylamino; those mercapto-substituted, such as 2-thio-ethylamino; and the like.

Examples of the di-unsubstituted C1-C12 alkylamino group in R ₃ include an amino group substituted with any two “unsubstituted C1-C12 alkyl” moieties in the mono-unsubstituted C1-C12 alkylamino group. About requirements, such as the range of preferable carbon number, it may be the same as a mono unsubstituted C1-C12 alkylamino group. Specific examples include dimethylamino, diethylamino and the like.

Sulfo group in R _3, a carboxy group, an alkoxy group, a carbamoyl group, a cyano group, an anilino group, an amino group, mono-unsubstituted C1-C4 alkyl group, di unsubstituted C1-C4 alkyl amino group, a phenoxy group, hydroxy group, The di-C1-C12 alkylamino group substituted with a group selected from the group consisting of a phenyl group and a mercapto group includes any two of the mono-C1-C12 alkylamino groups substituted with the corresponding substituents described above. Examples include amino groups substituted with a “substituted C1-C12 alkyl” moiety. The two “substituted C1-C12 alkyl” moieties may be different from each other but are preferably the same.
Specific examples include sulfo-substituted ones such as di (2-sulfoethyl) amino and di (3-sulfopropyl) amino; di (carboxymethyl) amino, di (2-carboxyethyl) amino and di (4-carboxybutyl) ) Carboxyl-substituted ones such as amino, di (5-carboxypentyl) amino, di (6-carboxyhexyl) amino; Alkoxy-substituted ones such as di (2-methoxyethyl) amino; Di (2-aminocarbonylethyl) Carbamoyl substituted such as amino; Cyano substituted such as di (2-cyanoethyl) amino; Anilino substituted such as di (2-phenylaminoethyl) amino; Amino substituted such as di (aminoethyl) amino Mono-unsubstituted C1-C4 alkylamino substituted such as di (N-methylaminoethyl) amino; di (N, N- Di (unsubstituted C1-C4 alkyl) amino substituted such as methylaminoethyl) amino; Phenoxy substituted such as di (2-phenoxyethyl) amino; Hydroxy substituted such as di (2-hydroxyethyl) amino A phenyl-substituted one such as dibenzylamino; a mercapto-substituted one such as di (2-thioethyl) amino;

Sulfo group, carboxyl group, unsubstituted C1-C4 alkyl group, unsubstituted C1-C4 alkoxy group, carbamoyl group, cyano group, anilino group, amino group, mono-unsubstituted C1-C4 alkylamino group, di-unsubstituted in R ₃ The anilino group substituted with a group selected from the group consisting of a C1-C4 alkylamino group, a phenoxy group, a hydroxy group, a phenyl group, and a mercapto group usually has 1 to 3 substituents, preferably One or two, more preferably one is mentioned.
Specific examples include sulfo-substituted ones such as 2-sulfoanilino and 3-sulfoanilino; carboxy-substituted ones such as 2-carboxyanilino and 3-carboxyanilino; and unsubstituted C1-substituents such as 3-methylanilino and 4-butylanilino. C4 alkyl substituted; unsubstituted C1-C4 alkoxy substituted such as 2-methoxyanilino; carbamoyl substituted such as 2-aminocarbonylanilino; cyano substituted such as 2-cyanoanilino; 2-phenylamino Anilino-substituted ones such as anilino; amino-substituted ones such as 4-aminoanilino; mono-unsubstituted C1-C4 alkylamino-substituted ones such as 4-methylaminoanilino and 3-ethylaminoanilino; 3,5- Di-unsubstituted C1-C4 alkyl such as dimethylaminoanilino and 3,5-diethylaminoanilino Mino-substituted; Phenoxy-substituted such as 2-phenoxyanilino; Hydroxy-substituted such as 3-hydroxymethylanilino; Phenyl-substituted such as 4-phenylanilino; Mercapto such as 4-mercaptoanilino And the like.

Examples of the unsubstituted C1-C10 alkylthio group for R ₃ include straight-chain or branched-chain groups, and straight-chain groups are preferred. As carbon number, it is C1-C10 normally, Preferably it is C1-C8, More preferably, it is C1-C6.
Specific examples include straight chain such as methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio; isopropylthio, Branched chain such as isobutylthio, isopentylthio, isohexylthio; and the like.

Sulfo group, carboxyl group, unsubstituted C1-C4 alkoxy group, carbamoyl group, cyano group, anilino group, amino group, mono-unsubstituted C1-C4 alkylamino group, di-unsubstituted C1-C4 alkylamino group, phenoxy in R ₃ As the C1-C10 alkylthio group substituted with a group selected from the group consisting of a group, a hydroxy group, a phenyl group, and a mercapto group, the above substituents are usually 1 to 3, preferably 1 or 2 More preferably, one substituted one is mentioned. As carbon number, it is C1-C10 normally, Preferably it is C1-C8, More preferably, it is C1-C6.
Specific examples include sulfo-substituted compounds such as 2-sulfoethylthio and 3-sulfopropylthio; carboxy-substituted compounds such as 2-carboxyethylthio, 4-carboxybutylthio, 5-carboxypentylthio and 6-carboxyhexylthio. Unsubstituted C1-C4 alkoxy substituted such as 2-methoxyethylthio; Carbamoyl substituted such as 2-aminocarbonylethylthio; Cyano substituted such as 2-cyanoethylthio; 2-phenylaminoethylthio Amino-substituted ones such as aminopropylthio; mono-unsubstituted C1-C4 alkylamino-substituted ones such as N-propylaminoethylthio; di-non-substituted ones such as N, N-dipropylaminoethylthio Substituted C1-C4 alkylamino-substituted; phenoxy such as 2-phenoxyethylthio Those substituted; 2-hydroxyethyl those hydroxy-substituted thio and the like; benzylthio intended phenyl substituted (phenyl methylthio) or the like, in that the 2-Chioechiruchio such mercapto substituted; and the like.

From a sulfo group, a carboxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a carbamoyl group, a cyano group, an anilino group, an amino group, a phenoxy group, a hydroxy group, a phenyl group, and a mercapto group in R ₃ Examples of the phenylthio group substituted with a group selected from the group include those in which the above-mentioned substituents are usually substituted by 1 to 3, preferably 1 or 2, more preferably 1.
Specific examples include sulfo-substituted compounds such as 2-sulfophenylthio and 3-sulfophenylthio; carboxy-substituted compounds such as 2-carboxyphenylthio and 3-carboxyphenylthio; 3-methylphenylthio and 4-butyl. Unsubstituted C1-C4 alkyl substituted such as phenylthio; Unsubstituted C1-C4 alkoxy substituted such as 2-methoxyphenylthio; Carbamoyl substituted such as 2-aminocarbonylphenylthio; 2-cyanophenylthio etc. Cyano-substituted ones; anilino-substituted ones such as 2-phenylaminophenylthio; amino-substituted ones such as 4-aminophenylthio; phenoxy-substituted ones such as 2-phenoxyphenylthio; 2-hydroxyethylphenylthio and the like Hydroxy-substituted ones such as 4-phenylphenylthio Ones; 4-mercaptomethyl intended mercapto-substituted phenyl thio, and the like; and the like.

From a sulfo group, a carboxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a carbamoyl group, a cyano group, an anilino group, an amino group, a phenoxy group, a hydroxy group, a phenyl group, and a mercapto group in R ₃ Examples of the phenoxy group substituted with a group selected from the group include those having 1 to 3, preferably 1 or 2, and more preferably 1 of the above substituents.
Specific examples include sulfo-substituted ones such as 2-sulfophenoxy and 3-sulfophenoxy; carboxy-substituted ones such as 2-carboxyphenoxy and 3-carboxyphenoxy; unsubstituted such as 3-methylphenoxy and 4-butylphenoxy C1-C4 alkyl substituted; unsubstituted C1-C4 alkoxy substituted such as 2-methoxyphenoxy; carbamoyl substituted such as 2-aminocarbonylphenoxy; cyano substituted such as 2-cyanophenoxy; 2-phenyl Anilino substituted such as aminophenoxy; amino substituted such as 4-aminophenoxy; phenoxy substituted such as 3-phenoxyphenoxy and 4-phenoxyphenoxy; hydroxy substituted such as 3-hydroxyphenoxy; 4-phenyl Phenyl-substituted ones such as phenoxy Those mercapto-substituted, such as 4-mercapto-phenoxy; and the like.

As the mono C1-C10 alkylamino C1-C10 alkylamino group in R ₃ , a linear or branched one can be mentioned, and a straight chain is preferable. The carbon number of each alkyl moiety is usually C1-C10, preferably C1-C6, and more preferably C1-C4.
Specific examples include 2-methylaminoethylamino, 3-methylaminopropylamino, 3-ethylaminopropylamino and the like.
The di-C1-C10 alkylamino C1-C10 alkylamino group for R ₃ may be one having independently two “monoalkyl” moieties of the above monoalkylaminoalkylamino group. The requirements such as the number of carbon atoms of the alkyl moiety may be the same.
Specific examples include 3- (N, N-diethylamino) propylamino, 2- (N, N-diethylamino) ethylamino and the like.

Among the above, R ₃ is a chlorine atom; an unsubstituted C 1-10 alkylamino group; a C1-C10 alkylamino group substituted with a sulfo group or a carboxy group; an unsubstituted C1-10 alkylthio group; a sulfo group, a carboxy group Or a C 1-10 alkylthio group substituted with an amino group; a phenylthio group substituted with a carboxy group; or a phenoxy group substituted with a carboxy group. More preferably, it is a C1-C10 alkylamino group substituted with a chlorine atom or a carboxy group. More preferably, it is a C1-C10 alkylamino group substituted with a chlorine atom or a carboxy group.

  In the above formula (1), a to d represent the substitution positions of two sulfo groups whose substitution positions are not specified. The substitution position of the two sulfo groups is not particularly limited, but a and d, or a and c are preferable, and a and c are more preferable.

Among the anthrapyridone compounds of the present invention represented by the above formula (1), preferred are the compounds represented by the above formula (2).
In the above formula (2), n, R _{1 to} R ₃ , and a to d have the same meaning as in the above formula (1), including preferable ones.

In the above formula (2), the bonding position between the pyridine ring whose bonding position is not specified and the adjacent carbonyl group may be any of the 2-position, 3-position, and 4-position with the nitrogen atom of the pyridine ring being the first position. Is preferably in the 3rd or 4th position, and more preferably in the 4th position.
On the other hand, the substitution position of R ₁ whose binding position is not specified is not particularly limited.

Regarding n, R _{1 to} R ₃ , and a to d in the above formulas (1) and (2), a compound in which preferable ones are combined is more preferable, and a compound in which more preferable ones are combined is more preferable. The same applies to more preferable ones, particularly preferable ones.

Specific examples of particularly preferable combinations in the above formula (1) include: n is 1, X is a pyridine ring, R ₁ is a hydrogen atom, R ₂ is an unsubstituted C1-C4 alkyl group, R ₃ is a chlorine atom, or a carboxy group A C1-C10 alkylamino group substituted with, and a combination in which the substitution positions of two sulfo groups whose substitution positions are not specified are a and c.

  The salt of the compound represented by the above formula (1) is a salt with an inorganic or organic cation. Among them, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts, and preferred inorganic salts are lithium, sodium, potassium salts, and ammonium salts. Examples of organic cation salts include, but are not limited to, salts with quaternary ammonium compounds represented by the following formula (3). Moreover, a free acid and those various salts may be a mixture. For example, any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt, and ammonium salt may be used.

In the above formula (3), Z _{1 to} Z ₄ each independently represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, or a hydroxyalkoxyalkyl group, and at least one is a group other than a hydrogen atom.

Examples of the alkyl group in Z _{1 to} Z ₄ in the formula (3) include methyl, ethyl and the like, and examples of the hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxy Propyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. Examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 3-hydroxyethoxy. Examples include butyl and 2-hydroxyethoxybutyl.

  Among these, preferred are sodium, potassium, lithium, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine salts, ammonium salts and the like. Of these, particularly preferred are lithium, ammonium, and sodium salts.

As is apparent to those skilled in the art, the salt of the compound represented by the above formula (1) can be easily obtained by the following method or the like.
For example, sodium chloride is added to a reaction solution containing the compound represented by the formula (1), or an aqueous solution in which a wet cake or a dried pigment is dissolved, salted out, and the precipitated solid is filtered to obtain the above formula ( The sodium salt of the compound represented by 1) can be obtained as a wet cake.
Moreover, after dissolving the obtained sodium salt wet cake in water, an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is separated by filtration, whereby the compound represented by the above formula (1) Or a mixture of a free acid and a sodium salt, in which a part of the compound represented by the formula (1) is a sodium salt.
Furthermore, while stirring the wet cake of the free acid of the compound represented by the formula (1) with water, for example, potassium hydroxide, lithium hydroxide, ammonia water, or water of the compound represented by the above formula (3) If an alkali is added by adding an oxide or the like, a corresponding potassium salt, lithium salt, ammonium salt, or quaternary ammonium salt can be obtained. By limiting the number of moles of the above-mentioned salts to be added relative to the number of moles of free acid, for example, mixed salts of lithium salt and sodium salt, and further mixed salts of lithium salt, sodium salt, ammonium salt, etc. Is possible. The salt of the compound represented by the above formula (1) may change the physical properties such as solubility or the ink performance when used as an ink depending on the type of the salt. Further, when a plurality of salts and the like are contained, a mixture having physical properties suitable for the purpose can be obtained by changing the ratio. For this reason, it is also preferable to appropriately select the type of salt according to the intended ink performance.

  Specific examples of the anthrapyridone compound represented by the formula (1) of the present invention are shown in Table 1 below, but the present invention is not limited thereto. In addition, in formula (1), the substitution positions of two sulfo groups whose substitution positions are not specified are the positions a and c in any of the specific examples.

The anthrapyridone compound of the present invention is produced, for example, by the following method. In the following formulas (4) to (7) and formula (A), n, X, R _{1 to} R ₃ , and a to d all have the same meaning as in formula (1).
1 mol of an anthraquinone compound represented by the following formula (4) obtained according to a known method described in JP-B-7-45629 and the like, and represented by R ₁ —X—C (O) CH ₂ COOR Β-ketoester derivative (wherein R represents a linear C1-C4 alkyl group, preferably methyl or ethyl) in a polar solvent such as xylene in a basic solvent such as sodium carbonate. A target compound represented by the following formula (5) is obtained by reacting at 130 to 180 ° C. for 5 to 15 hours in the presence of the compound.

  1 mol of metaaminoacetanilide is added to 1 mol of the obtained compound of the above formula (5) in an aprotic polar organic solvent such as N, N-dimethylformamide and a base such as sodium carbonate and copper acetate. In the presence of a copper catalyst, condensation is performed by performing an Ullmann reaction at 110 to 150 ° C. for 2 to 6 hours to obtain a compound represented by the following formula (6).

  The compound represented by the above formula (6) is sulfonated at 50 to 120 ° C. in 8 to 15% fuming sulfuric acid, and at the same time, the acetyl group is removed to obtain the compound represented by the following formula (7).

1 mol of the compound represented by the above formula (7) and 2 to 2.5 mol of the compound represented by the following formula (A), for example, in water at pH 2-9, 2-15 ° C., 30 minutes a compound represented by the following formula obtained by reacting 1 hour (8), the compound corresponding to _{R 3,} that is, the compound 2-5 mole, represented by _"R 3 -H" or the like, pH 7-10, By reacting at 20 to 90 ° C. for 10 minutes to 10 hours and substituting the leaving group Y in formula (8) with R ₃ , the compound represented by the above formula (1) can be obtained. The compound represented by the following formula (8), when a nitrogen atom is present as a ring-constituting atom of the heteroaromatic ring represented by X, can be represented by the nitrogen atom and hydrochloric acid purified by the progress of the reaction or the formula (A) The represented compound itself may form a salt.

The anthrapyridone compound of the present invention can be used as a magenta dye for dyeing natural and synthetic fiber materials or blended products, and the compound is suitable for the production of inks for writing and in particular ink jet recording ink compositions. ing.
When the compound represented by the above formula (1) is used as a dye to be contained in the ink composition, a metal cation chloride (for example, sodium chloride) and a sulfate (such as sodium chloride) contained in the total mass of the dye. For example, it is preferable to use an inorganic substance such as sodium sulfate), that is, a substance having a small content of “inorganic impurities”. The standard of the content is, for example, about 1% by mass or less, and the lower limit may be less than the detection limit of the analytical instrument, that is, 0%. In order to produce a pigment having a small amount of inorganic impurities, for example, a desalting treatment may be performed by a method using a known reverse osmosis membrane. In addition, a dried product or wet cake of the compound of the present invention or a salt thereof is suspended and purified by stirring in a mixed solvent of C1-C4 alcohol such as methanol and water, and the solid is separated by filtration and dried. You may desalinate.
The ink composition of the present invention is obtained by dissolving the compound represented by the above formula (1) in water or an aqueous solvent (water containing a water-soluble organic solvent described later). The reaction liquid containing the compound represented by can be used directly in the production of the ink composition. In addition, the compound can be isolated from the reaction solution by, for example, crystallization, spray drying, or the like and then dried as necessary, and an ink composition can be prepared using the obtained compound. The ink composition of the present invention is generally 0.1 to 20% by mass, preferably 1 to 15% by mass, more preferably 2 to 10% by mass, as a pigment, of the compound of the present invention in the total mass of the ink composition. contains.

  The ink composition of the present invention is prepared using water as a medium, and may contain a water-soluble organic solvent as necessary within a range that does not impair the effects of the present invention. The water-soluble organic solvent may function as a dye solubilizer, a drying inhibitor (wetting agent), a viscosity modifier, a penetration accelerator, a surface tension modifier, an antifoaming agent, etc., and the ink composition of the present invention. It is preferable to contain them. Examples of other ink preparation agents include known additions such as antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble UV absorbers, water-soluble polymer compounds, dye solubilizers, and surfactants. Agents. The ink composition of the present invention may contain 0 to 30% by mass of a water-soluble organic solvent, preferably 5 to 30% by mass, and 0 to 7% by mass of an ink preparation agent with respect to the total mass. The remainder other than the above is water.

Specific examples of the water-soluble organic solvent that can be used in the present invention include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; N, N -Carboxylic acid amides such as dimethylformamide and N, N-dimethylacetamide; Lactams such as 2-pyrrolidone and N-methyl-2-pyrrolidone; 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydro Cyclic ureas such as pyrimido-2-one; ketones or keto alcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1, 2 -Or 1,3-propylene glycol, 1,2- Is mono having C2-C6 alkylene units such as 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, Oligo, or polyalkylene glycol or thioglycol; polyol (triol) such as glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether (butyl carbitol), triethylene glycol monomethyl ether, trie C1-C4 alkyl ethers of polyhydric alcohol such as glycol monoethyl ether; .gamma.-butyrolactone, dimethyl sulfoxide and the like. These water-soluble organic solvents are used alone or in combination.
Among these, preferred are 2-pyrrolidone, N-methyl-2-pyrrolidone, mono, di, or triethylene glycol and dipropylene glycol, more preferably 2-pyrrolidone, N-methyl 2-pyrrolidone, diethylene glycol, Isopropanol and butyl carbitol.

Hereinafter, the ink preparation agent that can be used in preparing the ink composition of the present invention will be described.
Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts.
An example of the organic halogen compound is sodium pentachlorophenol.
Examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide.
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, 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 and antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate and the like.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink within the range of 8.0 to 11.0 without adversely affecting the prepared ink. For example, alkanolamines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. And carbonates.

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

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

  Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone, sulfonated benzotriazole, and the like.

  Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines, polyimines, and the like.

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

  Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants.

  Specific examples of the anionic surfactant include alkyl sulfonate, alkyl carboxylate, α-olefin sulfonate, polyoxyethylene alkyl ether acetate, N-acyl amino acid and its salt, N-acylmethyl taurate, Alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfone Acid salts, diethylsulfosuccinate, diethylhexylsylsulfosuccinate, dioctylsulfosuccinate and the like.

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

  Specific examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, Examples include imidazoline derivatives.

Specific examples of nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether and the like. Ether type: polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc. Ester series; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, -Acetylene glycol (alcohol) type such as dimethyl-1-hexyn-3-ol (for example, trade name Surfinol 104, 105, 82, 465, Olphine STG, etc., manufactured by Nissin Chemical); Polyglycol ether type (for example, , SIGMA-ALDRICH, Tergitol 15-S-7, etc.);
These ink preparation agents are used alone or in combination.

  In the aqueous ink composition of the present invention, the anthrapyridone compound of the present invention represented by the formula (1) is dissolved in water or the aqueous solvent (water containing a water-soluble organic solvent) together with the ink preparation agent and the like. Can be manufactured.

  In the above production method, the order of dissolving the components is not particularly limited. The dye may be dissolved in water or the aqueous solvent in advance, and the ink preparation agent may be added and dissolved. Alternatively, after the dye is dissolved in water, the aqueous solvent and the ink preparation agent may be added and dissolved. Also, the order may be different from this, or an ink composition may be produced by adding an aqueous solvent and an ink preparation agent to a reaction solution of a dye or a solution subjected to a desalting treatment with a reverse osmosis membrane. In preparing the ink composition, the water to be used is preferably water with few impurities such as ion exchange water and distilled water. Furthermore, if necessary, fine filtration may be performed using a membrane filter or the like to remove impurities. In particular, when it is used as an ink for ink jet recording, it is preferable to perform microfiltration. The pore diameter of the filter for performing microfiltration is usually 1 to 0.1 μm, preferably 0.8 to 0.1 μm.

  The magenta ink composition containing the water-soluble anthrapyridone compound of the present invention as a pigment is suitable for use in printing, copying, marking, writing, drawing, stamping, or a recording method, particularly ink jet recording. In this case, a high-quality magenta recorded image having good resistance to humidity, water, sunlight, ozone gas, friction and the like can be obtained. Further, by blending the compound of the present invention with a publicly known and used pigment such as yellow or magenta, the color tone of orange or red can be finely adjusted to achieve a color tone of your choice. It can also be used for toning when expressing other colors, particularly black.

  The colored product of the present invention is a substance colored with the anthrapyridone compound of the present invention or an ink composition containing the compound. The substance to be colored is not particularly limited, and examples thereof include, but are not limited to, paper, fiber, cloth (cellulose, nylon, wool, etc.), leather, and a color filter base material. Examples of the coloring method include a printing method such as dip dyeing, textile printing, screen printing, and a method using an ink jet printer, and a method using an ink jet printer is preferable.

  Examples of the recording material (media) to which the ink jet recording method of the present invention can be applied include information transmission sheets such as paper and film, fibers, leather, and the like, and information transmission sheets are preferable. The information transmission sheet is preferably a surface-treated sheet, specifically, an ink receiving layer provided on these substrates. The ink receiving layer is formed by, for example, impregnating or coating the base material with a cationic polymer; a porous white inorganic substance capable of absorbing a pigment in ink such as porous silica, alumina sol, or special ceramics, such as polyvinyl alcohol or polyvinyl pyrrolidone. Coating the surface of the base material together with the hydrophilic polymer. A paper provided with such an ink receiving layer is usually called ink jet exclusive paper (film) or glossy paper (film), for example, Pictolico Co., Ltd., trade name Pictolico; Canon Inc., trade name Professional Photo Paper , Super Photo Paper, Matte Photo Paper; Seiko Epson Co., Ltd. Photo Paper (Glossy), Photo Matte Paper, Superfine Glossy Film; Nihon Hewlett Packard Co., Premium Plus Photo Paper, Premium Glossy Film, Photo Paper; Konica Minolta Holdings Co., Ltd., Photo-like QP; Of course, plain paper can also be used.

  Among these, it is known that an image recorded on a recording material coated with a porous white inorganic substance has a particularly large discoloration due to ozone gas. However, the aqueous magenta ink composition of the present invention is resistant to ozone gas. Therefore, even when recording on such a recording material, an excellent effect that the color fading is extremely small is exhibited.

  Porous white inorganic materials used for such purposes include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite , Barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinc carbonate and the like.

  In order to record on a recording material by the ink jet recording method of the present invention, a container containing the ink composition of the present invention is loaded into a predetermined position of an ink jet printer, the ink composition is used as an ink, What is necessary is just to record on a to-be-recorded material by the normal method of discharging a droplet according to a recording signal. In the ink jet recording method of the present invention, in addition to the magenta ink composition of the present invention, each known ink composition such as yellow, cyan, further green, orange, blue (or violet), and the like, as needed A black ink composition or the like can be used in combination. The ink composition of each color is injected into each container, and these containers are used by being loaded into a predetermined position of the ink jet printer in the same manner as the container containing the ink composition of the present invention. Examples of the ink jet printer include a piezo method using mechanical vibration; a bubble jet (registered trademark) method using bubbles generated by heating; and the like.

  The water-based magenta ink composition of the present invention has a clear magenta color, and particularly in inkjet glossy paper, the recorded image has various fastness properties, that is, light resistance, ozone gas resistance, moisture resistance, water resistance, and the like. Excellent balance between resistance and ozone gas resistance. A recorded matter using the anthrapyridone compound of the present invention as a magenta ink for ink-jet recording has a magenta hue with high definition without selecting a recording material (paper, film, etc.). Moreover, it is highly safe for humans.

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

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. Each operation such as reaction and crystallization in the examples was carried out with stirring unless otherwise specified. Moreover, the maximum absorption wavelength (λmax) of the dyes obtained in the examples was measured in an aqueous solution, and the measured value was described.
In addition, when the amount of the target compound was not obtained by one synthesis reaction, the synthesis reaction was repeatedly performed until the amount of the target compound was obtained.

[Example 1]
(Process 1)
30.2 parts of ethyl isonicotiate and 20.4 parts of sodium ethoxide were sequentially added to 26.4 parts of ethyl acetate, and reacted at 40 ° C. for 9 hours. 110 parts of water was added to the reaction solution, adjusted to pH 7.0 with 35% hydrochloric acid, and extracted with diethyl ether. The organic layer was concentrated under reduced pressure to obtain 20.6 parts of an oily compound represented by the following formula (9).

(Process 2)
In 45 parts of xylene, 15.8 parts of a compound represented by the following formula (10), 1.1 parts of sodium carbonate, and 19.3 parts of a compound represented by the above formula (9) were sequentially added, and the temperature was raised. The reaction was carried out at a temperature of 130 ° C. for 14 hours. Meanwhile, ethanol and water produced by the reaction were distilled out of the system while azeotroping with xylene to complete the reaction. Next, the reaction solution was cooled, 20 parts of methanol was added at 30 ° C. and stirred for 30 minutes, and then the precipitated solid was separated by filtration. The obtained solid was washed with 100 parts of methanol and then with 200 parts of warm water and then dried to obtain 21.3 parts of a compound represented by the following formula (11) as a yellow needle-like solid.

(Process 3)
In 37.4 parts of N, N-dimethylformamide, 17.8 parts of the compound represented by the above formula (11), 18.0 parts of metaaminoacetanilide, 5.8 parts of copper acetate monohydrate, and sodium carbonate 3.1 parts were sequentially added, the temperature was raised to 120 to 130 ° C., and the reaction was performed for 6 hours. The reaction solution was cooled to about 50 ° C., 120 parts of methanol was added, and the mixture was stirred for 30 minutes. The precipitated solid was separated by filtration, washed with 200 parts of methanol and then with warm water at 80 ° C., and then dried to obtain 15.3 parts of a compound of the following formula (12) as dark red crystals.

(Process 4)
12.5 parts of 32.5% fuming sulfuric acid was added to 13.4 parts of 98% sulfuric acid while cooling with water to prepare 30 parts of 10% fuming sulfuric acid. Under water cooling, 5.1 parts of the compound represented by the above formula (12) was added at 40 ° C. or lower, and then the temperature was raised to 80 to 85 ° C. and reacted for 7 hours. The reaction solution was added to 100 parts of ice water, and while the ice was added, the rise in the solution temperature due to heat generation was kept at 40 ° C. or lower. Further, water was added to make the liquid volume 250 parts, and this liquid was filtered to remove insoluble matters. While maintaining the obtained mother liquor at 60 to 65 ° C., 37.8 parts of sodium chloride was added and stirred for 2 hours, and the precipitated solid was separated by filtration. By washing with 200 parts of a 22% aqueous sodium chloride solution and drying, 6.3 parts of a dark red solid of a compound represented by the following formula (13) was obtained.

(Process 5)
In 70 parts of water, 6.8 parts of the compound represented by the above formula (13) was added, and 13.6 parts of chloroacetyl chloride was added dropwise under ice cooling. During that time, the liquid temperature was kept at 10 ° C. or lower and the pH was 1.0 to 2.0, and the reaction was carried out for 2 hours after the completion of the dropping. In addition, 25% sodium hydroxide aqueous solution was used for pH adjustment. The solid precipitated in the reaction solution was separated by filtration, and water was thoroughly squeezed to obtain 21.3 parts of a wet cake of a compound represented by the following formula (14). In addition, although the obtained wet cake was estimated to be a mixture containing the hydrochloride salt of the compound represented by the following formula (14), it was subjected to the next (step 6) reaction without any particular purification. .

(Step 6)
21.3 parts of the wet cake containing the compound represented by the formula (14) obtained in the above (Step 5) is dissolved in water so that the total amount becomes 75 parts, and further 17.8 parts of 6-aminohexanoic acid is added. added. This solution was heated to 50 to 55 ° C. and reacted for 10 hours while maintaining a pH of 10.0 using a 25% aqueous sodium hydroxide solution, then adjusted to pH 4.0 using 35% hydrochloric acid, and ammonium chloride 15. 4 parts were added and stirred for 2 hours. The mixture is allowed to cool to room temperature, the precipitated solid is separated by filtration, washed with 100 parts of a 24% aqueous ammonium chloride solution, and then thoroughly squeezed and dried to give sodium and ammonium salts of the compound represented by the following formula (15). As a result, 0.4 part of a dark red solid was obtained.
[lambda] max: 533 nm.

[Example 2]
[(A) Preparation of ink]
Using the compound represented by the formula (15) obtained in Example 1 above, an ink composition shown in Table 2 below was prepared, and an ink for evaluation was obtained by filtering with a 0.45 μm membrane filter. It was. As the “water” in Table 2, ion-exchanged water was used, including those for diluting ammonia water. The ink composition was prepared by adding water and a 2.8% aqueous ammonia solution so that the pH of the ink composition was 8 to 10 and the total amount was 100 parts. This ink preparation is referred to as Example 2.

[Comparative Example 1]
For comparison, in the same manner as in Example 2 except that the compound represented by the following formula (16) disclosed in Example 1 (3) of Patent Document 13 was used instead of the compound obtained in Example 1. Ink was prepared. This ink preparation is referred to as Comparative Example 1.

[Comparative Example 2]
A comparative ink was prepared in the same manner as in Example 2 except that the compound represented by the formula (13) obtained in (Step 4) of Example 1 was used. This ink preparation is referred to as Comparative Example 2.

[(B) Inkjet recording]
Each ink prepared in Example 2 and Comparative Examples 1 and 2 was subjected to inkjet recording on four types of glossy paper having an ink receiving layer containing a porous white inorganic substance using an inkjet printer (Pixus iP4100 manufactured by Canon Inc.). Went. During ink jet recording, an image pattern was created so that the print density was obtained with several levels of gradation, and a recorded matter was obtained. Using this as a test piece for evaluation, the following test was performed. The glossy paper used is as follows.
Glossy paper 1: Product name Professional Photo Paper manufactured by Canon Inc.
PR-101
Glossy paper 2: Canon Inc., trade name Glossy Gold
GL-101
Glossy paper 3: Epson, trade name Krispia Glossy paper 4: HP, trade name Advanced Photo Paper

[(C) Evaluation of recorded image]
Using each test piece obtained in (B) above, the following (D) ozone gas resistance test and (E) moisture resistance test were performed.

[(D) Ozone gas resistance test]
Each test piece was allowed to stand for 24 hours in an environment having an ozone concentration of 10 ppm, a humidity of 60% RH, and a temperature of 24 ° C. using an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.). For the gradation part where the D value before the test is around 1.2, the D value before and after the test is measured, and the residual ratio of the dye before and after the test is (D value after the test / D value before the test) × 100 = The residual rate (%) was calculated. The larger the remaining rate, the better.
The results are shown in Table 3 below.

[(E) Moisture resistance test]
Each test piece was left in an environment of 30 ° C. and 80% RH for 168 hours using a thermo-hygrostat (manufactured by Applied Giken Sangyo Co., Ltd.). About the gradation part whose D value before a test is 1.7 vicinity, the bleeding property before and behind a test was determined visually and evaluated in the following three steps.
○: No bleed is observed Δ: Slight bleed is observed ×: Large bleed is observed The results are shown in Table 4 below.

From Table 3, the residual rate in the ozone gas resistance test is almost the same as that in Example 2 and Comparative Example 1 in all glossy papers, but is extremely higher than that in Comparative Example 2. From the above results, it can be seen that the ozone gas resistance of Example 2 is extremely superior to that of Comparative Example 2.
Further, from Table 4, as for the moisture resistance test, Example 2 and Comparative Example 2 showed almost the same performance, but they were better than Comparative Example 1 without bleeding.
From the above results, it is clear that the anthrapyridone compound of the present invention is a dye that gives an image having fastness that is excellent in the balance between ozone gas resistance and moisture resistance as compared with known dyes. It is extremely suitable as a magenta dye for use.

Claims (23)

An anthrapyridone compound represented by the following formula (1) or a salt thereof.

[In Formula (1),
n represents an integer of 1 to 3,
X represents a heteroaromatic ring,
R ₁ represents a hydrogen atom, a carboxy group, a sulfo group, a phenyl group, an unsubstituted C1-C6 alkyl group, an unsubstituted C1-C6 alkoxy group, or a hydroxy group,
R ₂ is a hydrogen atom, an unsubstituted C1-C10 alkyl group, a hydroxy C1-C6 alkyl group, a mono C1-C10 alkylamino C1-C10 alkyl group, a di-C1-C10 alkylamino C1-C10 alkyl group, or a cyano C1- Represents a C6 alkyl group,
R ₃ represents a chlorine atom; a mono-unsubstituted C1-C12 alkylamino group; a sulfo group, a carboxy group, an alkoxy group, a carbamoyl group, a cyano group, an anilino group, an amino group, a mono-unsubstituted C1-C4 alkylamino group, a di-non group A mono C1-C12 alkylamino group substituted with a group selected from the group consisting of a substituted C1-C4 alkylamino group, a phenoxy group, a hydroxy group, a phenyl group, and a mercapto group; a di-unsubstituted C1-12 alkylamino group; Sulfo group, carboxy group, alkoxy group, carbamoyl group, cyano group, anilino group, amino group, mono-unsubstituted C1-C4 alkylamino group, di-unsubstituted C1-C4 alkylamino group, phenoxy group, hydroxy group, phenyl group, And a diC1-C12 alkylamino group substituted with a group selected from the group consisting of mercapto groups An unsubstituted anilino group; a sulfo group, a carboxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a carbamoyl group, a cyano group, an anilino group, an amino group, a mono-unsubstituted C1-C4 alkylamino group; An anilino group substituted with a group selected from the group consisting of a di-unsubstituted C1-C4 alkylamino group, a phenoxy group, a hydroxy group, a phenyl group, and a mercapto group; an unsubstituted C1-C10 alkylthio group; a sulfo group, a carboxy group Unsubstituted C1-C4 alkoxy group, carbamoyl group, cyano group, anilino group, amino group, mono-unsubstituted C1-C4 alkylamino group, di-unsubstituted C1-C4 alkylamino group, phenoxy group, hydroxy group, phenyl group, And a C1-C10 alkylthio group substituted with a group selected from the group consisting of a mercapto group; Phenylthio group; from sulfo group, carboxy group, unsubstituted C1-C4 alkyl group, unsubstituted C1-C4 alkoxy group, carbamoyl group, cyano group, anilino group, amino group, phenoxy group, hydroxy group, phenyl group, and mercapto group A phenylthio group substituted with a group selected from the group consisting of: an unsubstituted phenoxy group; a sulfo group, a carboxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a carbamoyl group, a cyano group, an anilino group, A phenoxy group substituted with a group selected from the group consisting of an amino group, a phenoxy group, a hydroxy group, a phenyl group, and a mercapto group; a mono C1-C10 alkylamino C1-C10 alkylamino group; or a diC1-C10 alkylamino A C1-C10 alkylamino group;
a to d represent the substitution positions of two sulfo groups whose substitution positions are not specified. ]   2. The anthrapyridone compound or a salt thereof according to claim 1, wherein the heteroaromatic ring in X is a 5-membered or 6-membered heteroaromatic ring.   The anthrapyridone compound or a salt thereof according to claim 1 or 2, wherein the heteroaromatic ring in X is a 5-membered or 6-membered nitrogen-containing heteroaromatic ring containing 1 or 2 nitrogen atoms as ring-constituting atoms.   The anthrapyridone compound or a salt thereof according to any one of claims 1 to 3, wherein X is a pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, furan ring, benzothiazole ring, thiazole ring, or imidazole ring.   The anthrapyridone compound or a salt thereof according to any one of claims 1 to 3, wherein X is a pyridine ring, a pyrazine ring, a pyridazine ring, or a pyrimidine ring. n is 1 or 2,
The anthrapyridone compound or a salt thereof according to any one of claims 1 to 5, wherein R ₂ is a hydrogen atom or an unsubstituted C1-C4 alkyl group. The anthrapyridone compound or a salt thereof according to any one of claims 1 to 6, which is represented by the following formula (2).

[In the formula (2), n, R _{1 to} R ₃ , and a to d represent the same meaning as in the formula (1). ]. The anthrapyridone compound or a salt thereof according to any one of claims 1 to 7, wherein R ₁ is a hydrogen atom, a sulfo group, or an unsubstituted C1-C6 alkyl group. The anthrapyridone compound or a salt thereof according to any one of claims 1 to 8, wherein R ₁ is a hydrogen atom.   The anthrapyridone compound or a salt thereof according to any one of claims 1 to 9, wherein the substitution positions of two sulfo groups whose substitution positions are not specified are a and c. R ₃ is a chlorine atom; unsubstituted C1-10 alkylamino group; C1-C10 alkylamino group substituted with sulfo group or carboxy group; unsubstituted C1-10 alkylthio group; substituted with sulfo group, carboxy group, or amino group The anthrapyridone compound or a salt thereof according to any one of claims 1 to 10, which is a substituted C1-10 alkylthio group; a phenylthio group substituted with a carboxy group; or a phenoxy group substituted with a carboxy group. n is 1,
X is a pyridine ring,
R ₁ is a hydrogen atom,
R ₂ is an unsubstituted C1-C4 alkyl group,
R ₃ is a C1-C10 alkylamino group substituted with a chlorine atom or a carboxy group,
The anthrapyridone compound or a salt thereof according to claim 1, wherein the substitution positions of two sulfo groups whose substitution positions are not specified are a and c.   An ink composition comprising the anthrapyridone compound or a salt thereof according to any one of claims 1 to 12.   The ink composition according to claim 13, further comprising water and a water-soluble organic solvent.   The content of the inorganic impurity in the compound or the salt thereof is 1 mass relative to the total mass of the anthrapyridone compound or the salt thereof according to any one of claims 1 to 12 contained as a pigment in the ink composition. The ink composition according to claim 13, which is not more than%.   The content of the anthrapyridone compound or a salt thereof according to any one of claims 1 to 12 contained as a pigment in the ink composition is 0.1 to 20% by mass relative to the total mass of the ink composition. The ink composition according to claim 13, wherein   The ink composition according to claim 13, which is for inkjet recording.   An ink jet recording method using the ink composition according to any one of claims 13 to 17 as ink, ejecting a droplet of the ink according to a recording signal, and attaching the ink droplet to a recording material to perform recording.   The inkjet recording method according to claim 18, wherein the recording material is an information transmission sheet.   The ink jet recording method according to claim 19, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance.   A colored body colored with the ink composition according to any one of claims 13 to 17.   The colored body according to claim 21, wherein coloring is performed by an ink jet printer.   An inkjet printer loaded with a container containing the ink composition according to any one of claims 13 to 17.