WO2010084741A1 - Anthrapyridone compound or salt thereof, magenta ink composition, and colored material - Google Patents

Abstract

Disclosed is a magenta dye (an anthrapyridone compound or a salt thereof) which is highly soluble in water, has a color and clarity suitable for inkjet recording, and enables the production of a recorded matter having excellent fastness including excellent light resistance and excellent gas resistance. Also disclosed is an ink composition comprising the magenta dye. The anthrapyridone compound is represented by formula (1). In the formula, X represents an pyridine ring, or the like; R₁ represents a hydrogen atom, or the like; R₂ represents an alkyl group, or the like; R₃ represents an unsubstituted alkyl group, or the like; and a to e independently represent a substitution position for a sulfo group or a sulfonyl group having a group R₃ of which the substitution position is not specified.

Description

Anthrapyridone compound or salt thereof, magenta ink composition, and colored product

The present invention relates to a novel anthrapyridone compound or a salt thereof, a magenta ink composition containing the 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 attached to various recording materials (paper, film, fabric, etc.) according to a recording signal for recording. In this method, since the recording head and the recording material are not in contact with each other, no sound 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 small OA printers to large industrial printers, and various robustnesses such as water resistance, moisture resistance, light resistance, and gas resistance of recorded images are required more than ever. ing.
Water resistance has been greatly improved by coating the surface of paper 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 and the like. .
Moisture resistance refers to resistance to a phenomenon in which a dye of an image oozes when a colored image is stored in an atmosphere of high humidity. 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 this azo dye, those with excellent sharpness and light resistance have been developed, but the light resistance is still inferior to other hue dyes such as cyan dye and yellow dye represented by copper phthalocyanine dye. 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), but all of hue, sharpness, light resistance, water resistance, gas resistance, and solution stability are all included. Nothing that satisfies the requirements has been obtained.

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) Japanese Patent Laid-Open No. 2000-256587 (pages 1-3 and 7-18) JP 2001-72884 A (pages 1-2 and 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) Japanese Patent Laying-Open No. 2005-314514 (pages 1-3 and 15-20) International Publication No. 2006/0775706 Pamphlet International Publication No. 2008/018495 Pamphlet

An object of the present invention is to provide a magenta dye (compound) which is suitable for ink jet recording and excellent in various fastness properties such as ozone gas resistance and moisture resistance of a recorded image, and an ink composition containing the same.

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. .

That is, the present invention
1)
An anthrapyridone compound represented by the following formula (1) or a salt thereof,

[In Formula (1),
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 represents 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 is an unsubstituted C1-C12 alkyl group; aryl group, heterocyclic group, sulfo group, carboxy group, alkoxycarbonyl group, acyl group, carbamoyl group, cyano group, alkoxy group, phenylalkoxy group, phenoxy group, hydroxy group And a C1-C12 alkyl group substituted with a group selected from the group consisting of nitro group; unsubstituted aryl group; halogen atom, cyano group, hydroxy group, sulfo group, unsubstituted alkyl group, carboxy group, alkoxycarbonyl group An aryl group substituted with a group selected from the group consisting of carbamoyl group, alkoxy group, phenoxy group, and nitro group; unsubstituted heterocyclic group; or halogen atom, cyano group, hydroxy group, sulfo group, unsubstituted alkyl Group, carboxy group, alkoxycarbonyl group, carbamoyl group, alkoxy group A heterocyclic group substituted with a group selected from the group consisting of: a phenoxy group, and a nitro group;
a to e each represent a substitution position of a sulfo group whose substitution position is not specified or a sulfonyl group having R ₃ . ]

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 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,
5)
The anthrapyridone compound or a salt thereof according to any one of 1) to 4) above, wherein R ₂ is a hydrogen atom or an unsubstituted C1-C4 alkyl group,

6)
The anthrapyridone compound or a salt thereof according to any one of 1) to 5) represented by the following formula (2):

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

7)
The anthrapyridone compound or a salt thereof according to any one of 1) to 6) above, wherein R ₁ is a hydrogen atom;
8)
The anthrapyridone compound or a salt thereof according to any one of 1) to 7) above, wherein the substitution position of the sulfo group whose substitution position is not specified is a, and the substitution position of the sulfonyl group having R ₃ is c ,
9)
The anthrapyridone compound or a salt thereof according to any one of 1) to 8) above, wherein R ₃ is an unsubstituted C1-C12 alkyl group; or a phenyl group substituted with a sulfo group or a carboxy group;
10)
The anthrapyridone compound or a salt thereof according to any one of 1) to 9) above, wherein R ₃ is an unsubstituted C1-C6 alkyl group; or a phenyl group substituted with a sulfo group or a carboxy group;
11)
X is a pyridine ring,
R ₁ is a hydrogen atom,
R ₂ is an unsubstituted C1-C4 alkyl group,
R ₃ is an unsubstituted C1-C8 alkylamino group,
The anthrapyridone compound or a salt thereof according to 1) above, wherein the substitution position of the sulfo group whose substitution position is not specified is a, and the substitution position of the sulfonyl group having R ₃ is c,
12)
X is a pyridine ring,
R ₁ is a hydrogen atom,
R ₂ is a methyl group,
R ₃ is an n-hexyl group,
The anthrapyridone compound or a salt thereof according to 1) above, wherein the substitution position of the sulfo group whose substitution position is not specified is a, and the substitution position of the sulfonyl group having R ₃ is 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)
13) The content of the inorganic impurity in 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 is 1% by mass or less. The ink composition according to claim 1,
16)
The content of the anthrapyridone compound or a salt thereof according to any one of the above 1) to 12) 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 attached to a recording material to perform 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 is characterized by excellent water solubility and good filterability with respect to a membrane filter in the course of producing an ink composition. A recorded image using the anthrapyridone compound or a salt thereof of the present invention as a magenta ink for inkjet recording has a magenta hue without selecting a recording material (paper, film, etc.). Further, the magenta ink composition containing the compound of the present invention or a salt thereof may be recorded on a recording material coated with a porous white inorganic material on the surface, such as a photographic image-quality inkjet paper (film). Various fastness properties, particularly ozone gas resistance and moisture resistance are extremely good, and the long-term storage stability of photographic-tone recorded images is excellent. 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. Hereinafter, for the sake of convenience, the term “anthrapyridone compound of the present invention” will be simply described, including both “the anthrapyridone compound of the present invention or a salt thereof”.
The anthrapyridone compound of the present invention is a water-soluble magenta dye. 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), 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, and pyrimidine are preferable, and pyridine is more 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), examples of the unsubstituted C1-C6 alkyl group for R ₁ include straight-chain or branched-chain groups, and straight-chain is preferable. The number of carbon atoms is usually C1-C6, preferably C1-C4. Specific examples include straight-chain compounds such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; branched chains such as isopropyl, isobutyl, 2-methylbutyl, and t-butyl; 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. The number of carbon atoms is usually C1-C6, preferably C1-C4. Specific examples include straight chain such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy and n-hexyloxy; branched chain such as isopropoxy, isobutoxy and t-butoxy; It is done.

Among the above, R ₁ is preferably a hydrogen atom, a sulfo group, or an unsubstituted C1-C6 alkyl group, and more 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. The number of carbon atoms is usually C1-C10, preferably C1-C6, more preferably 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; 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 carbons is usually C1-C6, preferably C2-C4. Specific examples include straight chain such as 2-hydroxyethyl, 3-hydroxypropyl and 4-hydroxybutyl; branched chain such as 2-hydroxy-1,2-dimethylethyl; and the like.

Examples of the mono C1-C10 alkylamino C1-C10 alkyl group for R ₂ include straight-chain or branched-chain groups, with straight-chain being preferred. 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 the straight-chain is preferable. The number of carbon atoms is usually C1-C6, preferably C1-C4. Specific examples include cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, cyanohexyl and the like.

Of 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 unsubstituted C1-C12 alkyl group for R ₃ include those in which the alkyl portion is linear, branched or cyclic, preferably linear or branched, and more preferably linear. . The number of carbon atoms is usually C1-C12, preferably C1-C8, more preferably C1-C6.
Specific examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and the like. Straight chain; branched chain such as isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, neopentyl, t-pentyl, isohexyl, 2-ethylhexyl; cyclic such as cyclopropyl, cyclopentyl, cyclohexyl; etc. Is mentioned.

Selected from the group consisting of aryl group, heterocyclic group, sulfo group, carboxy group, alkoxycarbonyl group, acyl group, carbamoyl group, cyano group, alkoxy group, phenylalkoxy group, phenoxy group, hydroxy group and nitro group in R ₃ The C1-C12 alkyl group substituted with the above group is any one of the above-mentioned substituent groups, and usually 1 to 3, preferably 1 or 2, more preferably 1 is substituted. Can be mentioned. When there are a plurality of substituents, the types of substituents may be the same or different.
The alkyl moiety may be linear or branched, and is preferably linear. The alkyl moiety usually has C1-C12, preferably C1-C8, more preferably C1-C6.

Examples of the C1-12 alkyl group substituted with the aryl group in R ₃ include those in which the aryl group is a C6-C14 aryl group such as phenyl, naphthyl, and anthracenyl, with the phenyl group being preferred. Specific examples include phenyl-substituted ones such as benzyl, 3-phenylpropyl, 6-phenylhexyl and 12-phenyldodecyl; naphthyl-substituted ones such as naphthylmethyl, 3-naphthylpropyl, 6-naphthylhexyl and 12-naphthyldodecyl. Thing; etc. are mentioned.

Examples of the C1-C12 alkyl group substituted with the heterocyclic group in R ₃ include those usually substituted with a 6-membered heteroaromatic ring, preferably a nitrogen-containing 6-membered heteroaromatic ring, and more preferably substituted with pyridine. There is no restriction on the substitution position, and substitution may be performed at any position of the C1-C12 alkyl group. Further, the substitution position on the heterocyclic group is not limited. For example, when the heterocyclic group is pyridine, the substitution position on the pyridine is the 2-position, 3-position, 4-position with the nitrogen atom as the 1-position. Either is acceptable. Specific examples include pyridylmethyl, pyridylethyl, pyridylpropyl, pyridylbutyl, pyridylpentyl, pyridylhexyl, pyridyldecyl, pyridyldecyl and the like.

Examples of the C1-C12 alkyl group substituted with a sulfo group in R ₃ include 2-sulfoethyl, 6-sulfohexyl, 12-sulfododecyl and the like.

Examples of the C1-C12 alkyl group substituted with a carboxy group in R ₃ include 6-carboxyhexyl, 12-carboxydodecyl and the like.

Examples of the C1-C12 alkyl group substituted with an alkoxycarbonyl group in R ₃ include those substituted with a C1-C4 alkoxycarbonyl group, preferably a linear C1-C4 alkoxycarbonyl group. Specific examples include 6-ethoxycarbonylhexyl, 3-methoxycarbonylpropyl, 2-butoxycarbonylpentyl and the like.

Examples of the C1-C12 alkyl group substituted with an acyl group in R ₃ include those substituted with a linear C1-C3 alkylcarbonyl group or a phenyl C1-C3 alkylcarbonyl group. Specific examples include 6-methylcarbonylhexyl, 5- (2-phenylethylcarbonyl) pentyl and the like.

Examples of the C1-C12 alkyl group substituted with a carbamoyl group in R ₃ include 5-carbamoylpentyl, 6-carbamoylhexyl, 10-carbamoyldecyl and the like.

Examples of the C1-C12 alkyl group substituted with a cyano group in R ₃ include 3-cyanopropyl, 6-cyanohexyl, 12-cyanododecyl and the like.

Examples of the C1-C12 alkyl group substituted with an alkoxy group in R ₃ include those substituted with a linear or branched chain, preferably a linear C1-C4 alkoxy group. Specific examples include 5-butoxypentyl, 6-methoxyhexyl, 10-methoxydecyl, 12-methoxydodecyl and the like.

Examples of the C1-C12 alkyl group substituted with a phenylalkoxy group in R ₃ include those substituted with a phenylC1-C3 alkoxy group, preferably a benzyloxy (phenylmethoxy) group. Specific examples include 6-benzyloxyhexyl, 12-benzyl oxide decyl and the like.

Examples of the C1-C12 alkyl group substituted with a phenoxy group in R ₃ include 4-phenoxybutyl, 6-phenoxyhexyl, 12-phenoxide dodecyl and the like.

Examples of the C1-C12 alkyl group substituted with a hydroxy group in R ₃ include 4-hydroxybutyl, 6-hydroxyhexyl, 12-hydroxydodecyl and the like.

Examples of the C1-C12 alkyl group substituted with the nitro group in R ₃ include 3-nitropropyl, 6-nitrohexyl, 12-nitrododecyl and the like.

Examples of the unsubstituted aryl group for R ₃ include a phenyl group and a naphthyl group, and a phenyl group is preferable.

Substituted with a group selected from the group consisting of a halogen atom, a cyano group, a hydroxy group, a sulfo group, an unsubstituted alkyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, an alkoxy group, a phenoxy group, and a nitro group in R ₃ Examples of the aryl group include a phenyl group or a naphthyl group substituted with 1 to 3, preferably 1 or 2, and more preferably 1 of the above substituents, and a phenyl group is preferable. When there are a plurality of substituents, the types of substituents may be the same or different.

Examples of the aryl group substituted with a halogen atom in R ₃ include those substituted with a chlorine atom, a bromine atom, a fluorine atom, or an iodine atom, preferably a chlorine atom. Specific examples include those substituted with a chlorine atom such as 2-chlorophenyl, 4-chlorophenyl, 2-chloronaphthyl, 4-chloronaphthyl; 2-bromophenyl, 4-bromophenyl, 2-bromonaphthyl, 4-bromonaphthyl, etc. Substituted with bromine atom; substituted with iodine atom such as 2-iodophenyl, 4-iodophenyl, 2-iodonaphthyl, 4-iodonaphthyl; 2-fluorophenyl, 4-fluorophenyl, 2-fluoronaphthyl, 4 -Fluorine atom-substituted ones such as fluoronaphthyl;

Examples of the aryl group substituted with a cyano group in R ₃ include 2-cyanophenyl, 4-cyanonaphthyl and the like.

Examples of the aryl group substituted with a hydroxy group in R ₃ include 2-hydroxyphenyl, 2-hydroxynaphthyl, 4-hydroxynaphthyl and the like.

Examples of the aryl group substituted with a sulfo group in R ₃ include 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 4-sulfonaphthyl and the like.

Examples of the aryl group substituted with an unsubstituted alkyl group in R ₃ include those substituted with a linear or branched chain, preferably a linear unsubstituted C1-C4 alkyl group. Specific examples include 2-methylphenyl, 3-ethylphenyl, 4-butylphenyl, 2-methylnaphthyl, 4-ethylnaphthyl and the like.

Examples of the aryl group substituted with a carboxy group in R ₃ include 2-carboxyphenyl, 4-carboxyphenyl, 2-carboxynaphthyl, 4-carboxynaphthyl and the like.

Examples of the aryl group substituted with an alkoxycarbonyl group in R ₃ include those substituted with a linear or branched chain, preferably a linear C1-C4 alkoxy group. Specific examples include 2-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 2-butoxycarbonylnaphthyl, 4-methoxycarbonylnaphthyl and the like.

Examples of the aryl group substituted with the carbamoyl group in R ₃ include 2-carbamoylphenyl, 4-carbamoylphenyl, 2-carbamoylnaphthyl, 4-carbamoylnaphthyl and the like.

Examples of the aryl group substituted with an alkoxy group in R ₃ include those substituted with a linear or branched chain, preferably a linear C1-C4 alkoxy group. Specific examples include 2-methoxyphenyl, 3-butoxyphenyl, 4-ethoxyphenyl, 2-ethoxynaphthyl, 4-methoxynaphthyl and the like.

Examples of the aryl group substituted with a phenoxy group in R ₃ include 4-phenoxyphenyl, 2-phenoxynaphthyl, 4-phenoxynaphthyl and the like.

Examples of the aryl group substituted with the nitro group in R ₃ include 2-nitrophenyl, 4-nitrophenyl, 3-nitrophenyl, 2-nitronaphthyl, 4-nitronaphthyl and the like.

Examples of the unsubstituted heterocyclic group for R ₃ include 2-, 3-, and 4-pyridyl groups.

Substituted with a group selected from the group consisting of a halogen atom, a cyano group, a hydroxy group, a sulfo group, an unsubstituted alkyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, an alkoxy group, a phenoxy group, and a nitro group in R ₃ Examples of the heterocyclic group include a pyridyl group substituted with 1 to 3, preferably 1 or 2, more preferably 1 of the above substituents. When there are a plurality of substituents, the types of substituents may be the same or different. The substitution position on the heterocyclic group of the substituent selected from the above group and the bonding position between the sulfur atom in formula (1) and the heterocyclic group may be any position, but both Both positions are limited to carbon atoms in the heterocyclic group and are not heteroatoms. Further, the positions of both are not the same.

Examples of the heterocyclic group substituted with a halogen atom in R ₃ include those substituted with a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, preferably a chlorine atom. Specific examples include 4-chloro-2-pyridyl, 6-chloro-2-pyridyl, 4-bromo-2-pyridyl, 6-bromo-2-pyridyl, 4-fluoro-2-pyridyl, and 6-fluoro-2. -Pyridyl, 4-iodo-2-pyridyl, 6-iodo-2-pyridyl, 2-chloro-4-pyridyl, 2-bromo-4-pyridyl, 2-iodo-4-pyridyl, 2-fluoro-4-pyridyl Etc.

Examples of the heterocyclic group substituted with a cyano group in R ₃ include 4-cyano-2-pyridyl, 6-cyano-2-pyridyl, 2-cyano-4-pyridyl and the like.

Examples of the heterocyclic group substituted with a hydroxy group in R ₃ include 4-hydroxy-2-pyridyl, 6-hydroxy-2-pyridyl, 2-hydroxy-4-pyridyl and the like.

Examples of the heterocyclic group substituted with a sulfo group in R ₃ include 4-sulfo-2-pyridyl, 6-sulfo-2-pyridyl, 2-sulfo-4-pyridyl and the like.

Examples of the heterocyclic group substituted with an unsubstituted alkyl group in R ₃ include 4-methyl-2-pyridyl, 5-ethyl-3-pyridyl, 6-methyl-4-pyridyl and the like.

Examples of the heterocyclic group substituted with a carboxy group in R ₃ include 4-hydroxy-2-pyridyl, 6-carboxy-2-pyridyl, 2-hydroxy-4-pyridyl and the like.

Examples of the heterocyclic group substituted with an alkoxycarbonyl group in R ₃ include those substituted with a linear or branched chain, preferably a linear C1-C3 alkoxy group. Specific examples include 4-methoxycarbonyl-2-pyridyl, 6-methoxycarbonyl-3-pyridyl, 6-ethoxycarbonyl-2-pyridyl and the like.

Examples of the heterocyclic group substituted with a carbamoyl group in R ₃ include 4-carbamoyl-2-pyridyl, 6-carbamoyl-3-pyridyl, 6-carbamoyl-4-pyridyl and the like.

Examples of the heterocyclic group substituted with an alkoxy group in R ₃ include those substituted with a linear or branched chain, preferably a linear C1-C4 alkoxy group. Specific examples include 4-methoxy-2-pyridyl, 6-butoxy-3-pyridyl, 6-ethoxy-4-pyridyl and the like.

Examples of the heterocyclic group substituted with a phenoxy group in R ₃ include 4-phenoxy-2-pyridyl, 6-phenoxy-3-pyridyl, 6-phenoxy-4-pyridyl and the like.

Examples of the heterocyclic group substituted with a nitro group in R ₃ include 4-nitro-2-pyridyl, 6-nitro-3-pyridyl, 6-nitro-4-pyridyl and the like.

Of the above, R ₃ is preferably an unsubstituted C1-C12 alkyl group; or a phenyl group substituted with a sulfo group or a carboxy group. More preferably, it is an unsubstituted C1-C6 alkyl group; or a phenyl group substituted with a sulfo group or a carboxy group.

In the formula (1), a to e each represent a substitution position of a sulfo group whose substitution position is not specified or a sulfonyl group having R ₃ . Although the substitution positions in both a to e are not limited, they are not substituted at the same position. Preferably, either one is substituted at the position a and the other is substituted at the position c. More preferably, the sulfo group is substituted at the position a and the sulfonyl group having R ₃ is substituted at the position c. .

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), R _{1 to} R ₃ and a to e have the same meaning as in the above formula (1), including preferred ones.

In the above formula (2), the bonding positions of the pyridine ring whose bonding position is not specified and the adjacent carbonyl group are the 2-position, 3-position, and 4-position, with the nitrogen atom of the pyridine ring being the 1-position, The position or the 4-position is preferable, and the 4-position is more preferable.
On the other hand, the substitution position of R ₁ whose substitution position is not specified is not particularly limited. Both positions are on the carbon atom of the pyridine ring and are not nitrogen atoms.

Regarding R _{1 to} R ₃ and a to e 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 preferable combinations in the above formula (1) include X as a pyridine ring, R ₁ as a hydrogen atom, R ₂ as an unsubstituted C1-C4 alkyl group, and R ₃ as an unsubstituted C1-C8 alkylamino group. Examples include a combination in which the substitution position of the sulfo group whose position is not specified is a and the substitution position of the sulfonyl group having R ₃ is c.
Further, specific examples of a more preferable combination include a substitution position of a sulfo group in which X is a pyridine ring, R ₁ is a hydrogen atom, R ₂ is a methyl group, R ₃ is an n-hexyl group, and the substitution positions are not specified. a, substitution position of the sulfonyl group having R ₃ is as combinations is 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. Depending on the type of salt, the physical properties such as solubility may differ, and if necessary, select the type of salt as appropriate. It is also possible to obtain a mixture having

[In 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 of them is a group other than a hydrogen atom. ]

In the formula (3), examples of the alkyl group in Z ₁ to Z ₄ include methyl, ethyl and the like. Examples of the hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. Examples of the hydroxyalkoxyalkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl and the like.

Among the above salts, preferred are sodium, potassium, lithium, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine salts, ammonium salts, and the like. More preferred salts 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 product of the compound is dissolved, salted out, and the precipitated solid is filtered, whereby 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 oxide or the like is added to make it alkaline, 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. For this reason, it is also preferable to 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, about the sulfo group whose substitution position in Formula (1) is not specified, and the sulfonyl group having R ₃ , the sulfo group is substituted at the position of a, and the sulfonyl group having R ₃ is at the position of c. It described about what has been substituted.

The anthrapyridone compound of the present invention is produced, for example, by the following method. In the following formulas (4) to (7), X, R _{1 to} R ₃ , and a to e all have the same meaning as in the above formula (1).
The anthrapyridone compound represented by the above formula (1) is obtained, for example, as follows.
That is, 1 mol of a compound represented by the following formula (4) and a β-ketoester represented by R ₁ —X—C (O) CH ₂ COOR (R may be, for example, an alkyl group such as methyl or ethyl). By reacting 1.1 to 3 mol of the derivative 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, it is represented by the following formula (5). To obtain a compound.

1 mol of the aniline having the R ₃ S group as a substituent is added to 1 mol of the compound represented by the above formula (5) in an aprotic polar organic solvent such as N, N-dimethylformamide. In the presence of a base such as sodium and a copper catalyst such as copper acetate, condensation is performed by carrying out 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 following formula (7) is obtained by oxidizing the sulfur atom in the compound represented by the above formula (6) by adding hydrogen peroxide in acetic acid at 50 to 80 ° C.

The anthrapyridone compound represented by the above formula (1) of the present invention can be obtained by sulfonation of the obtained compound represented by the above formula (7) by a conventional method in 5 to 15% fuming sulfuric acid.

The anthrapyridone compound of the present invention can be used as a magenta dye for dyeing natural and synthetic fiber materials or blends, and these compounds are used for the production of inks for writing and in particular ink jet recording ink compositions. Is suitable.
When the compound represented by the above formula (1) is used as a dye contained in the ink composition, a metal cation chloride (for example, sodium chloride) or a sulfate (for example, sodium sulfate) contained in the total amount of the dye. It is preferable to use inorganic substances such as), that is, those having a low 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. Further, the dried product or wet cake of the compound of the present invention or a salt thereof is stirred and suspended in a mixed solvent of C1-C4 alcohol such as methanol and water and crystallized, and the precipitated solid is separated by filtration and dried. A desalting treatment may be performed by a method such as

The ink composition of the present invention is an aqueous ink composition 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 (1), for example, the reaction liquid after completion of the final step in the synthesis reaction of the compound represented by formula (1), can be used directly in the production of the ink composition. I can do it. 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. In the ink composition of the present invention, the compound of the present invention is usually 0.1 to 20% by mass, preferably 1 to 15% by mass, more preferably 2 to 10% by mass as a pigment 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 and an ink preparation agent 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 the ink preparation agent include known additives such as antiseptic / antifungal agents, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, and surfactants. Can be mentioned. The ink composition of the present invention may contain 0 to 30% by mass, preferably 5 to 30% by mass of a water-soluble organic solvent, and 0 to 7% by mass of an ink preparation agent, based on 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 and 1,3-dimethylhexahydro Cyclic ureas such as pyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1,2 -Or 1,3-propylene glycol, 1,2- 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.
Of these, 2-pyrrolidone, N-methyl-2-pyrrolidone, mono-, di- or triethylene glycol, and dipropylene glycol are preferable, and 2-pyrrolidone, N-methyl 2-pyrrolidone, diethylene glycol, and isopropanol are more preferable. And butyl carbitol.

Hereinafter, the ink preparation agent will be described.
Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, 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 compounds include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-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 preventive include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

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

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

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-acyl methyl 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 alcohols such as dimethyl-1-hexyn-3-ol (for example, trade name Surfynol 104, 105, 82, 465, Orphine STG, etc., manufactured by Nissin Chemical); Polyglycol ethers (eg, SIGMA- And the like, such as Tergitol 15-S-7 manufactured by ALDRICH).
These ink preparation agents are used alone or in combination.

The ink composition of the present invention can be produced by dissolving the compound represented by the formula (1) in water or the aqueous solvent (water containing a water-soluble organic solvent) together with the ink preparation agent and the like.

In the above production method, there is no particular limitation on the order in which the components are dissolved. The dye may be dissolved in water or the aqueous solvent in advance, and the ink preparation agent may be added and dissolved, or after the dye is dissolved in water, the water-soluble organic solvent, the ink preparation agent, and the like are added and dissolved. Also good. 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 an ink jet printer, 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 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 above-described 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 dip dyeing method, a textile printing method, a printing method such as screen printing, a method using an ink jet printer, and the like, 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, etc., and information transmission sheets are preferred. 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; for example, porous alcohol, polyvinyl pyrrolidone, or the like, which is a porous white inorganic substance capable of absorbing pigments in ink such as porous silica, alumina sol, and special ceramics 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 images recorded on a recording material coated with a porous white inorganic material have particularly large discoloration due to ozone gas, but the ink composition of the present invention has excellent ozone gas resistance. For this reason, even when recording on such a recording material, an excellent effect of very little discoloration 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 the recording material by the ink jet recording method of the present invention, for example, a container containing the ink composition of the present invention is loaded in a predetermined position of the ink jet printer and recorded on the recording material by a normal method. Good. In the ink jet recording method of the present invention, in addition to the publicly known yellow and cyan, each ink composition of green, orange, blue (or violet) and the like, the magenta ink composition of the present invention, and optionally a black ink composition Can be used together with things. The ink composition of each color is injected into each container, and these containers may be 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 has a high clear hue particularly on inkjet glossy paper, and various fastnesses of recorded images, that is, light resistance, ozone gas resistance, moisture resistance, water resistance The nature is also high. 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; .

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 feature of good filterability. In addition, the ink composition of the present invention containing this compound or a salt thereof has good storage stability without solid precipitation, physical property change, color change and the like after long-term storage. A recorded matter using the anthrapyridone compound or a salt thereof 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.). Furthermore, the magenta ink composition of the present invention can 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 a photographic image-specific inkjet paper (film), various fastnesses such as light resistance, moisture resistance, ozone gas resistance, etc. The moisture resistance and ozone gas resistance are extremely good, and the long-term storage stability of photographic-tone recorded images is excellent. 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.

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.

[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, adjusted to pH 7.0 with 35% hydrochloric acid, extracted with diethyl ether, and then the organic layer was distilled off under reduced pressure to obtain 20.6 parts of an oily compound represented by the following formula (8). Got.

(Process 2)
In 45 parts of xylene, 15.8 parts of a compound represented by the following formula (9), 1.1 parts of sodium carbonate, and 19.3 parts of a compound represented by the above formula (8) 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 hot water and then dried to obtain 21.3 parts of a compound represented by the following formula (10) as a yellow needle-like solid.

(Process 3)
In 14.3 parts of N, N-dimethylformamide, 8.9 parts of the compound represented by the above formula (10), 8.4 parts of paraaminophenyl-n-hexylthioether, copper (II) acetate monohydrate 0 0.03 part and 3.9 parts of sodium acetate were sequentially added, and the temperature was raised to 125 to 130 ° C. over 1 hour, followed by reaction for 4 hours. The reaction solution was allowed to cool to 50 ° C., 60 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 100 parts of methanol and 200 parts of warm water at 80 ° C. and dried to obtain 9.0 parts of dark red crystals of the compound represented by the following formula (11).

(Process 4)
To 40 parts of acetic acid, 0.2 part of sodium tungstate dihydrate and 9.0 parts of the compound represented by the above formula (11) were added at 60 ° C. or lower, and the temperature was raised to 75-80 ° C. At this temperature, 3.5 parts of 30% hydrogen peroxide water was added dropwise over 10 minutes, and the reaction was further continued for 2 hours. A mixed solution of 23 parts of methanol and 14 parts of water was added to the obtained reaction liquid at 50 ° C. The obtained liquid was cooled to 30 ° C. and stirred for 16 hours, and then the precipitated solid was separated by filtration, washed with water and dried to obtain 8.9 parts of a compound represented by the following formula (12) as red crystals.

(Process 5)
41.3 parts of 31.9% fuming sulfuric acid was added to 48.7 parts of 98% sulfuric acid while cooling with water to prepare 90 parts of 12% fuming sulfuric acid. To the resulting fuming sulfuric acid, 8.9 parts of the compound represented by the above formula (12) was added at 10 ° C. or lower under water cooling, and then the temperature was raised to 50 to 55 ° C. and reacted for 2 hours. When the reaction solution was added to 150 parts of ice water and the temperature of the solution due to heat generation was kept below 40 ° C. while adding ice, a solid was precipitated. The precipitated solid was separated by filtration, washed with hot water at 60 ° C. and then with methanol and dried to obtain 8.0 parts of a dark red solid of the compound represented by the following formula (13).
λmax: 527 nm.

[Example 2]
[(A) Preparation of ink]
Using the compound represented by the formula (13) obtained in Example 1 above, an ink composition shown in Table 2 below was prepared, and filtered through a 0.45 μm membrane filter to obtain an ink for evaluation. 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]
Instead of the compound obtained in Example 1, the same procedure as in Example 2 was used except that the ammonium salt of the compound represented by the following formula (14) disclosed in Example 1 (3) of Patent Document 13 was used. A comparative ink was prepared. This ink preparation is referred to as Comparative Example 1.

[(B) Inkjet recording]
For each ink prepared in Example 2 and Comparative Example 1, inkjet recording was performed 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.). It was. During ink jet recording, an image pattern was prepared so that the print density was obtained with several gradations, 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 PR-101 manufactured by Canon Inc.
Glossy paper 2: manufactured by Canon, trade name Glossy Gold GL-101
Glossy paper 3: Epson, trade name Krispia Glossy paper 4: HP, trade name Advanced Photo Paper

[(C) Evaluation test 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 placed in an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.) and left for 24 hours in an environment with an ozone concentration of 10 ppm, a humidity of 60% RH, and a temperature of 24 ° C. 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 placed in a thermo-hygrostat (manufactured by Applied Giken Sangyo Co., Ltd.) and left in an environment of 30 ° C. and 80% RH for 168 hours. 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 much higher in Example 2 than in Comparative Example 1 in all glossy papers. From the above results, it can be seen that the ozone gas resistance of Example 2 is extremely superior to that of Comparative Example 1.
Also, from Table 4, with respect to the moisture resistance test, except for the result with glossy paper 3, Example 2 is 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 higher in ozone gas resistance and excellent in moisture resistance than known dyes. It is extremely suitable as a magenta dye for use.

Claims (23)

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

   

   [In Formula (1),
   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 represents 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 is an unsubstituted C1-C12 alkyl group; aryl group, heterocyclic group, sulfo group, carboxy group, alkoxycarbonyl group, acyl group, carbamoyl group, cyano group, alkoxy group, phenylalkoxy group, phenoxy group, hydroxy group And a C1-C12 alkyl group substituted with a group selected from the group consisting of nitro group; unsubstituted aryl group; halogen atom, cyano group, hydroxy group, sulfo group, unsubstituted alkyl group, carboxy group, alkoxycarbonyl group An aryl group substituted with a group selected from the group consisting of carbamoyl group, alkoxy group, phenoxy group, and nitro group; unsubstituted heterocyclic group; or halogen atom, cyano group, hydroxy group, sulfo group, unsubstituted alkyl Group, carboxy group, alkoxycarbonyl group, carbamoyl group, alkoxy group A heterocyclic group substituted with a group selected from the group consisting of: a phenoxy group, and a nitro group;
   a to e each represent a substitution position of a sulfo group whose substitution position is not specified or a sulfonyl group having R ₃ . ]
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.
3. 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 one or two nitrogen atoms as ring-constituting atoms.
4. 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.
5. The anthrapyridone compound or a salt thereof according to any one of claims 1 to 4, wherein R ₂ is a hydrogen atom or an unsubstituted C1-C4 alkyl group.
6. The anthrapyridone compound or a salt thereof according to any one of claims 1 to 5, which is represented by the following formula (2).
   

   

   [In Formula (2), R _{1 to} R ₃ and a to e represent the same meaning as in Formula (1). ]
7. The anthrapyridone compound or a salt thereof according to any one of claims 1 to 6, wherein R ₁ is a hydrogen atom.
8. The anthrapyridone compound or a salt thereof according to any one of claims 1 to 7, wherein the substitution position of the sulfo group whose substitution position is not specified is a, and the substitution position of the sulfonyl group having R ₃ is c.
9. The anthrapyridone compound or a salt thereof according to any one of claims 1 to 8, wherein R ₃ is an unsubstituted C1-C12 alkyl group; or a phenyl group substituted with a sulfo group or a carboxy group.
10. The anthrapyridone compound or a salt thereof according to any one of claims 1 to 9, wherein R ₃ is an unsubstituted C1-C6 alkyl group; or a phenyl group substituted with a sulfo group or a carboxy group.
11. X is a pyridine ring,
    R ₁ is a hydrogen atom,
    R ₂ is an unsubstituted C1-C4 alkyl group,
    R ₃ is an unsubstituted C1-C8 alkylamino group,
    The anthrapyridone compound or a salt thereof according to claim 1, wherein the substitution position of the sulfo group whose substitution position is not specified is a, and the substitution position of the sulfonyl group having R ₃ is c.
12. X is a pyridine ring,
    R ₁ is a hydrogen atom,
    R ₂ is a methyl group,
    R ₃ is an n-hexyl group,
    The anthrapyridone compound or a salt thereof according to claim 1, wherein the substitution position of the sulfo group whose substitution position is not specified is a, and the substitution position of the sulfonyl group having R ₃ is c.
13. An ink composition containing the anthrapyridone compound or a salt thereof according to any one of claims 1 to 12.
14. The ink composition according to claim 13, further comprising water and a water-soluble organic solvent.
15. The content of inorganic impurities in the total mass 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 1% by mass or less. The ink composition as described.
16. 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
17. The ink composition according to claim 13, which is for inkjet recording.
18. An ink jet recording method in which recording is performed by using the ink composition according to any one of claims 13 to 17 as ink, ejecting small droplets of the ink according to a recording signal, and attaching the ink droplet to a recording material.
19. The inkjet recording method according to claim 18, wherein the recording material is an information transmission sheet.
20. 20. 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.
21. A colored body colored with the ink composition according to any one of claims 13 to 17.
22. The colored body according to claim 21, wherein the 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 claims 13 to 17.