JP2008280467A - Water-soluble anthrapyridone compound or its salt, ink composition, and colored material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-soluble magenta pigment having a high dissolvability to water or a water-soluble organic solvent, a hue and a sharpness suitable for inkjet recording, a high color density, and the excellent solidity of a recorded matter, such as lightfastness, gas resistance, moisture resistance and waterfastness, and an ink composition containing the same having a good storage stability. <P>SOLUTION: Provided are the anthrapyridone compound represented by formula (1), (wherein R is a hydrogen atom or an alkyl group, Y is a mono- or dicarboxy-substituted anilino group, and X is a cross-linking group such as an N,N-hydrazinediyl) and a salt thereof. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a water-soluble anthrapyridone compound or a salt thereof, an ink composition containing the compound, and a colored product colored with the ink composition.

Among various color recording methods, a recording method using an inkjet printer, which is one of the representative methods, that is, inkjet printing, has developed various ink ejection methods, all of which generate ink droplets, This is attached to various recording materials, for example, paper, film, fabric, etc., and recording is performed. This method has been rapidly spreading in recent years because of the features that the recording head and the recording material are not in direct contact, so there is no sound generation and is quiet, and the size, speed and color are easy. Large growth is expected in the future. Conventionally, inks such as fountain pens, felt-tip pens, and ink jet print inks are inks in which a water-soluble dye is dissolved in an aqueous medium. In these water-based inks, ink marks at the pen tip and the ink discharge nozzle are used. In order to prevent clogging, a water-soluble organic solvent is generally added. These inks provide a recording image with sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, have little bleeding, and have excellent storage stability. Is required. The formed recorded image is required to have fastness such as water resistance, moisture resistance, light resistance, and gas resistance.
Ink-jet nozzle clogging occurs when the water content in the ink evaporates near other nozzles and other solvents and additives, and the dye crystallizes and precipitates when the composition state is low in water and high in solvents and additives. There are many things derived from this. Therefore, it is one of the very important required performances that crystals do not easily precipitate even when the ink is evaporated and dried. For this reason, high solubility in solvents and additives is one of the properties required for pigments.

  By the way, in order to record image or character information on a color display of a computer in color by an ink jet printer, generally a subtraction method using four colors of ink of yellow (Y), magenta (M), cyan (C), and black (K). Mixed colors are used, whereby the recorded image is expressed in color. In order to reproduce the additive color mixture image by red (R), green (G), and blue (B) on a CRT (CRT) display etc. as faithfully as possible with the subtractive color mixture image, each dye used in the ink, especially Y, It is desired that each of M and C has a hue close to a standard and is clear. Further, the ink is required to be stable against long-term storage, to have a high density of the printed image as described above, and to be excellent in fastness of the printed image.

  Due to recent developments in inkjet printing technology, the speed of printing has been dramatically improved, and the movement of using inkjet printers in the same way as laser printers using electronic toner for printing documents on plain paper, which is the main application in office environments. Is out. Ink jet printers have the advantage that the type of recording paper is not limited and the price of the machine is relatively low. In particular, ink jet printers are spreading in small to medium-sized office environments such as SOHO. Thus, when using an inkjet printer for printing on plain paper, hue and water resistance tend to be more important among various qualities required for printed matter. In order to satisfy these performances, particularly water resistance, a method of using a pigment ink has been proposed. However, an ink using a pigment has a problem that storage stability is poor, and a pigment is usually used as a solution. However, since the ink is used as an ink in which a solid pigment is dispersed, the problem that the nozzles of the printer head are clogged is relatively likely to occur. In addition, when pigment ink is used, there are many problems in terms of abrasion resistance, and the hue is often inferior to dyes. In contrast, in the case of an ink using a dye, the problem of an ink using such a pigment is relatively unlikely to occur. However, dye inks are particularly inferior in water resistance to pigment inks, and there is a strong desire for improvement.

Many proposals have been made for the problem of improving water resistance on plain paper. For example, an azo dye described in Patent Document 1 has been proposed as an ink-jet magenta dye having excellent water resistance and improved hue and light resistance.
Patent Documents 2 to 11 disclose anthrapyridone-based magenta dyes.
Patent Documents 12 and 13 disclose dimeric anthrapyridone-based magenta dyes bonded with a crosslinking group.

Japanese Patent No. 3396997 JP 2000-109464 A JP-A-10-306221 JP 2000-191660 A JP 2000-169776 A JP 2001-72884 A Japanese Patent Laid-Open No. 2001-139836 JP 2002-332418 A Japanese Patent Laying-Open No. 2005-8868 JP 2005-314514 A JP 2006-188706 A WO2003 / 027185 WO2006 / 075706

The azo dye described in Patent Document 1 is very excellent in water resistance on a specific plain paper, but it cannot be said that the water resistance is excellent in many kinds of various plain papers on the market. The application range is narrow.
Patent Documents 12 and 13 disclose magenta dyes excellent in water resistance and / or moisture resistance, but do not disclose any water resistance, particularly water resistance of a recorded image when recorded on plain paper.
Therefore, there has been a demand for a magenta dye that has excellent water resistance uniformly on more types of plain paper and also has excellent light resistance, hue, and color density.
The present invention has high solubility in water or a water-soluble organic solvent, has a hue and sharpness suitable for ink jet recording, has a high color density, and has light resistance, gas resistance, moisture resistance, and particularly water resistance of the recorded matter. It is an object of the present invention to provide a water-soluble magenta dye having excellent fastness such as the above and an ink composition containing the same and having good storage stability.

As a result of intensive investigations, the present inventors have found that a water-soluble anthrapyridone compound represented by a specific formula and an ink composition containing the same solve the above-described problem. The invention has been completed.
That is, the present invention
(1)
Anthrapyridone compound represented by the following formula (1) or a salt thereof

(Wherein R represents a hydrogen atom or an alkyl group, Y represents a mono- or dicarboxy-substituted anilino group, and X represents a bridging group).
(2)
R is a hydrogen atom or a C1-C4 alkyl group,
Y is a mono- or dicarboxy-substituted anilino group, and the bridging group X is N, N-hydrazinediyl or a group selected from the following formulas (2) to (8) or an anthrapyridone compound according to (1) or its salt,

(In the formula (2), n is 2 to 8)

(In formula (3), R ² represents a hydrogen atom or a methyl group)

(In formula (6), m represents 2 to 4)

(3)
R is a methyl group,
Y is a 3,5-dicarboxyanilino group or a 2,5-dicarboxyanilino group,
Formula (2) in which the bridging group X is N, N′-hydrazinediyl; n is represented by 2 to 6; Formula (3) in which R ² is a hydrogen atom or a methyl group; Formula (4); Formula (5); an anthrapyridone compound or a salt thereof according to (1) or (2), wherein m is a group selected from formula (6); formula (7); ,
(4)
R is a methyl group,
Y is a 3,5-dicarboxyanilino group;
Any one of (1) to (3), wherein the bridging group X is a formula (2) in which n is represented by 2 to 6; or a formula (3) in which R ² is a hydrogen atom or a methyl group An anthrapyridone compound or a salt thereof according to one item,
(5)
The anthrapyridone compound or a salt thereof according to any one of (1) to (4) represented by the following formula (9):

(6)
An ink composition containing the anthrapyridone compound or a salt thereof according to any one of (1) to (5);
(7)
The ink composition according to (6), comprising water and a water-soluble organic solvent;
(8)
The ink composition according to (7), which is for inkjet recording,
(9)
The ink composition according to any one of (6) to (8), wherein the content of inorganic impurities in the total amount of the anthrapyridone compound according to any one of claims 1 to 5 is 1% by weight or less. ,
(10)
The ink composition according to any one of (6) to (9), wherein the content of the anthrapyridone compound according to any one of claims 1 to 5 is 0.1 to 20% by weight or less.
(11)
In an ink jet recording method in which ink droplets are ejected in accordance with a recording signal to perform recording on a recording material, the ink composition according to any one of (6) to (10) is used as ink. Inkjet recording method,
(12)
The inkjet recording method according to (11), wherein the recording material is an information transmission sheet,
(13)
The ink jet recording method according to (12), wherein the information transmission sheet contains plain paper or an ink image-receiving layer containing a porous white inorganic substance,
(14)
(6) thru | or the colored body colored with the ink composition of any one of (10),
(15)
The colored product according to (14), wherein coloring is performed by an inkjet printer,
(16)
An inkjet printer filled with a container containing the ink composition according to any one of (6) to (10),
About.

The water-soluble anthrapyridone compound or salt thereof represented by the above formula (1) of the present invention is excellent in solubility in water or a water-soluble organic solvent. In addition, it has a feature of good filterability for, for example, a membrane filter in the process of producing an ink composition, and gives a magenta hue that is very clear and light on an inkjet recording paper. Further, the ink composition of the present invention containing this compound has very good storage stability without crystal precipitation, physical property change, hue change and the like after long-term storage. A printed matter using the ink composition of the present invention as an ink for ink jet recording is an ideal hue as a magenta hue without selecting a recording material (for example, paper, film, etc.), and a photographic color image Can be reproduced faithfully on paper.
In addition, the ink composition of the present invention has extremely improved water resistance especially on plain paper as compared with conventional dye inks. In addition, even when recording on a recording material coated with a porous white inorganic material such as paper for exclusive use for photographic image quality and film, various fastness properties, that is, gas resistance such as water resistance, moisture resistance, ozone gas resistance, etc. In addition, the light resistance is good, and the long-term storage stability of photographic-tone recorded images is also excellent. For this reason, the ink is very suitable for ink jet printing, which is one of the features that a recording medium is not selected. As described above, the water-soluble anthrapyridone compound of the above formula (1) is extremely useful as a magenta dye contained in an ink, particularly an ink for inkjet recording.

  The present invention will be described in detail. In the present specification, unless otherwise specified, acidic functional groups such as sulfo group and carboxy group are represented in the form of free acid.

The novel anthrapyridone compound of the present invention is represented by the formula (1).
In the formula (1), R represents a hydrogen atom or an alkyl group. As the alkyl group, for example, C1-C4 alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl and t-butyl are preferable. More preferably, it is a linear alkyl group.
Y represents a mono- or dicarboxy-substituted anilino group. Specific examples of Y include 4-carboxyanilino group, 3-carboxyanilino group, 2-carboxyanilino group, 3,5-dicarboxyanilino group, 2,5-dicarboxyanilino group and the like. It is done. Dicarboxy-substituted anilino is more preferable, 3,5-dicarboxyanilino and 2,5-dicarboxyanilino are still more preferable, and 3,5-dicarboxyanilino is particularly preferable.
As the bridging group X, N, N′-hydrazinediyl, the above formula (2), formula (3), formula (4), formula (5), formula (6), formula (7), and formula (8) Etc.
In the above formula (2), n is 2 to 8, preferably 2 to 6, and more preferably 2 to 4. Ethylene, propylene and butylene are preferred.
In the above formula (3), R ² is a hydrogen atom or methyl, and the hydrogen atom and methyl may be substituted one by one, but preferably both are hydrogen atoms or both are methyl. More preferably, both R ² are hydrogen atoms.
In said formula (6), m is 2 thru | or 4, and ethylene, propylene, and butylene are mentioned, All are preferable.

  Preferred as the crosslinking group X of the above formula (1) are the formula (2), the formula (3), the formula (4) and the formula (6), more preferably the formula (3), the formula (4) and the formula. (6), with formula (3) being particularly preferred.

  The compound which combined the preferable thing of said each group is more preferable, and the compound etc. which combined the more preferable thing are similarly more preferable.

  Specific examples of the compound represented by the formula (1) are shown in Table 1. In Table 1, (K) represents a carboxy group, and the number immediately before (K) represents the number of each substituent. That is, “3,5-2 (K) -anilino” represents “3,5-dicarboxyanilino”, and the others are the same.

  The compound of the above formula (1) exists also in the form of a free acid or a salt thereof. Examples of the salt of the compound of the above formula (1) include salts with inorganic or organic cations. Specific examples of the inorganic cation salt include ammonium salts and alkali metal salts such as lithium, sodium, potassium, and the like. Examples of organic cations include, but are not limited to, salts of compounds represented by the following formula (10).

(In Formula (10), Z < ¹ > -Z < ⁴ > is respectively independently a hydrogen atom, a (C1-C4) alkyl group, a hydroxy (C1-C4) alkyl group, or a hydroxy (C1-C4) alkoxy (C1-C4) alkyl group. Of these, the combination in which all of Z ^{1 to} Z ⁴ are hydrogen atoms is an ammonium salt.)

Here, examples of the alkyl group in which Z ^{1 to} Z ⁴ are alkyl include methyl, ethyl and the like; and examples of the hydroxyalkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxy Butyl, 3-hydroxybutyl, 2-hydroxybutyl and the like; and examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) Examples include butyl and 2- (hydroxyethoxy) butyl.

  Preferable examples of the salt include sodium, potassium, lithium, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine salt, and ammonium salt. Of these, particularly preferred are lithium, sodium, potassium and ammonium salts.

As will be apparent to those skilled in the art, the salt of the compound of the above formula (1) can be easily obtained by the following method.
For example, the reaction solution before adjusting the pH to 2 by adding concentrated hydrochloric acid in Example 1 described later, or a wet cake containing the compound of formula (1) or a dried product of the compound of formula (1) was dissolved. Sodium chloride is added to the aqueous solution for salting out, and the precipitated solid is filtered to obtain a sodium salt of the compound of the above formula (1) as a wet cake.
Further, 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 filtered to obtain the free acid of the compound of the above formula (1). Alternatively, a mixture of a free acid and a sodium salt in which a part of the compound of the formula (1) is a sodium salt can be obtained.
Further, while stirring the wet cake of the free acid of the compound of the formula (1) with water, for example, potassium hydroxide, lithium hydroxide, ammonia water or a hydroxide of the formula (10) is added to make it alkaline. For example, 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 salt to be added relative to the number of moles of free acid, for example, a mixed salt of lithium and sodium, and a mixed salt of lithium, sodium, potassium, and ammonium can be prepared. Is possible.
The salt of the compound of the above formula (1) may change the physical properties such as solubility or the performance of the ink when used as an ink, particularly the performance related to fastness, depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the target ink performance.

The following method can be used to obtain the compound of the above formula (1). In the following formulas (11) to (13) and (100), R, Y, and X have the same meaning as R in the formula (1).
For example, carboxy-substituted aniline corresponding to Y in the above formula (1) is 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol and 2,4,6-trichloro-s-triazine (cyanuric chloride). A compound obtained by subjecting 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, to a condensation reaction in water at pH 3 to 6, 0 to 25 ° C. for 2 to 4 hours is converted to the following formula (11 ) Is further subjected to a condensation reaction at pH 4 to 7, 50 to 70 ° C., for 2 to 5 hours to obtain a compound represented by the following formula (100).

Next, 0.5 to 1.0 mol, preferably 0.5 to 0.8 mol, of diamine corresponding to X in the formula (1) is reacted at pH 8 to 11, 70 to 95 ° C. for 1 to 5 hours. The target compound of the above formula (1) can be obtained.
The order of the condensation reaction may be determined as appropriate according to the reactivity of the compound to be condensed, and is not limited to the above order.

The compound of the said Formula (11) is obtained as follows, for example.
That is, 1 mol of a bromide represented by the following formula (12) and 1.1 to 5 mol of 5-acetylamino-2-sulfoaniline in an aprotic polar organic solvent such as DMF, sodium carbonate and the like and acetic acid In the presence of a copper catalyst such as copper, condensation is performed by performing an Ullmann reaction at 120 to 140 ° C. for 2 to 5 hours to obtain a compound of the following formula (13). Here, sodium carbonate or the like is used to neutralize the acid generated as the reaction proceeds.

  The obtained acetyl group of the formula (13) is removed by hydrolysis at 90 to 130 ° C. in the presence of a strong acid such as sulfuric acid to obtain the compound of the formula (11).

The dye of the above formula (1) of the present invention can be isolated as a solid free acid by addition of a mineral acid such as hydrochloric acid after the reaction, and the resulting free acid solid is converted into water or, for example, aqueous hydrochloric acid. Inorganic salts contained as impurities by washing with acidic water, such as chlorides of metal cations such as sodium chloride, alkali metal salts of sulfate cations such as sodium sulfate, etc. The “inorganic impurities” can be removed.
These inorganic impurities are used when preparing an ink composition and / or an ink containing the compound of the above formula (1), for storage stability of the ink, etc., and when performing ink jet recording using the ink. In many cases, it adversely affects the discharge stability and the like. Therefore, the content of the inorganic impurities in the total amount of the anthrapyridone compound represented by the above formula (1) is preferably at least 1% by weight, and the lower limit is 0% by weight, that is, the detection limit in the analytical instrument. It may be the following.
A method using a reverse osmosis membrane, for example, is known in order to produce a pigment with few inorganic impurities. As another method, a dried product or wet cake of the compound of the above formula (1) or a salt thereof is suspended in a mixed solvent of C1-C4 alcohol such as methanol and water and stirred, and then the solid is collected by filtration. The desalting treatment is also possible by drying.

The dye of the above formula (1) is suitable for dyeing natural and synthetic fiber materials or blended products, and also for producing writing ink and ink jet recording ink.
The reaction liquid containing the dye of the above formula (1) can also be used directly in the production of the ink composition of the present invention. However, after the compound is isolated from the reaction solution, for example, by drying the reaction solution by a method such as spray drying, the resulting dye can be processed into an ink composition. The ink composition of the present invention usually contains 0.1 to 20% by weight, more preferably 1 to 10% by weight, and still more preferably 2 to 8% by weight of the dye of the above formula (1) in an aqueous solution.

The ink composition of the present invention is prepared using water as a medium. If necessary, the ink composition may contain a water-soluble organic solvent and an ink preparation agent as long as the effects of the present invention are not impaired. Water-soluble organic solvents are used as dye solubilizers, drying inhibitors (wetting agents), viscosity modifiers, penetration enhancers, surface tension modifiers, antifoaming agents, and the like. Other ink preparation agents include, for example, antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventing agents, UV absorbers, viscosity adjusting agents, dye dissolving agents, antifading agents, emulsion stabilizers, surface tension adjusting agents. , Known additives such as antifoaming agents, dispersants, and dispersion stabilizers.
The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass, preferably 0 to 15% by mass, based on the entire ink. % Is good. The remainder other than the above is water.

  Examples of the water-soluble organic solvent include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; N, N-dimethylformamide or N, Amides such as N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido- Heterocyclic ketones such as 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- or 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, or thiodiglycol (C2-C6 ) Mono, oligo or polyalkylene glycols or thioglycols having alkylene units; polyols (triols) 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 monobutyl ether (butyl carbitol), triethylene glycol monome Ethers, polyvalent (C1 -C4) monoalkyl ethers of alcohols, such as triethylene glycol monoethyl ether; gamma-butyrolactone or dimethyl sulfoxide and the like.

  Preferred as the above water-soluble organic solvent are isopropanol, glycerin, mono, di or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone and butyl carbitol, more preferably isopropanol, Glycerin, diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone and butyl carbitol. These water-soluble organic solvents are used alone or in combination.

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 isothiazoline compounds 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 and the like It is done.
Other antiseptic / antifungal agents include sodium sorbate, sodium acetate and sodium benzoate. Other specific examples of antiseptic / antifungal agents include, for example, trade names Proxel GXL (S) and Proxel XL-2 (S) manufactured by Avecia.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink within the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. For example, 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 acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the ultraviolet absorber include a compound that emits fluorescence by absorbing ultraviolet rays represented by benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, or benzoxazole compounds, so-called fluorescence. Brighteners can also be used.

  Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

  Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like. It is preferred to use urea.

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

  Examples of the surface tension adjusting agent include a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant.

  Anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfates polyoxyalkyl ether sulfates Salt, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkyl allyl sulfonate, diethyl sulfosuccinate , Diethylhexylsyl sulfosuccinate, dioctyl sulfosuccinate and the like.

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

  Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and other imidazoline derivatives. There is.

  Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ethers such as alkyl ethers; polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monoole Esters such as ate and polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7- Acetylene glycol (alcohol) type such as all, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol (for example, trade name Surfy manufactured by Nisshin Chemical Co., Ltd.) Nord 104, 82, 465, Orphine STG, etc.).

  As the antifoaming agent, a highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based, or silicone-based compound is used as necessary.

  These ink preparation agents are used alone or in combination. The surface tension of the ink of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m. Similarly, the viscosity of the ink is preferably 30 mPa · s or less, and more preferably adjusted to 20 mPa · s or less.

In order to produce the ink composition of the present invention, there is no particular limitation on the order of dissolving each agent such as an additive. In preparing the ink composition, the water to be used is preferably one having few impurities such as ion exchange water or distilled water.
Furthermore, if necessary, microfiltration may be performed using a membrane filter to remove impurities. When used as ink for an inkjet printer, it is preferable to perform microfiltration. The pore diameter of the filter for performing microfiltration is usually 1 to 0.1 microns, preferably 0.8 to 0.2 microns.

  The ink composition containing the coloring matter of the present invention is suitable for use in printing, copying, marking, writing, drawing, stamping, or recording (printing), particularly in inkjet recording. In addition, the ink composition of the present invention is less likely to cause crystal precipitation even when dried in the vicinity of the nozzles of an ink jet printer, and for this reason, clogging of the head is also unlikely to occur. Furthermore, when the ink composition of the present invention is used for inkjet recording, a high-quality magenta-colored print having good resistance to water, light, ozone, nitrogen oxide gas, and friction can be obtained, particularly on plain paper. The water resistance of the recorded image is very good.

In some inkjet printers, two types of ink, a high-density ink and a low-density ink, are loaded in one printer for the purpose of supplying a high-definition image. In that case, an ink containing the dye of the present invention at a high concentration and an ink containing a low concentration may be prepared and used as an ink set. Moreover, you may use this pigment | dye only for either one.
Moreover, you may use together a well-known magenta dye in the range which does not inhibit effects, such as water resistance which the pigment | dye of this invention has.
The colorant of the present invention can also be used for toning of other colors, such as black ink, or for the purpose of preparing a red ink or blue (or violet) ink by mixing with a yellow colorant or a cyan colorant.

  The colored body of the present invention is a substance colored with the pigment of the present invention. There are no particular restrictions on the material of the colored body, for example, information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, base materials for color filters, etc. Anything is acceptable and not limited to these. 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.

The information transmission sheet is not particularly limited, and plain paper as well as surface-treated sheets, specifically, paper, synthetic paper, films and other substrates provided with an ink receiving layer are used. It is done. Here, the ink receiving layer is, for example, a method of impregnating or coating the base material with a cationic polymer; or inorganic fine particles capable of absorbing a pigment in ink such as porous silica, alumina sol, and special ceramics. A method of coating the surface of the substrate together with a hydrophilic polymer such as pyrrolidone; Those provided with such an ink receiving layer are usually called ink jet exclusive paper, ink jet exclusive film, glossy paper, or glossy film.
Plain paper means paper that is not particularly provided with an ink-receptive layer, and various papers are commercially available depending on the application. An example of commercially available plain paper includes: double-sided plain plain paper (manufactured by Seiko Epson Corporation); color plain paper (manufactured by Canon Inc.); Hewlett Packard). In addition, PPC paper whose use is not particularly limited to ink jet printing is also plain paper.
The ink composition of the present invention is particularly excellent in water resistance of images recorded on plain paper as described above, but is also excellent in resistance to other light, ozone, humidity and friction. On the other hand, the water resistance of the image recorded on the above-mentioned ink jet dedicated paper is very excellent, and similarly, the light resistance, gas resistance, moisture resistance and abrasion resistance are also excellent.

In order to record on a recording material by the ink jet recording method of the present invention, for example, a container filled with the above ink composition is set at a predetermined position of an ink jet printer, and recording is performed on the recording material by a normal method. Good.
In the ink jet recording method of the present invention, yellow, cyan, and optionally green, blue (or violet), red, and black inks can be used in combination with the ink composition of the present invention. In this case, the ink of each color is injected into each container, and these containers are used in a predetermined position of the ink jet printer.
Inkjet printers include, for example, a printer that uses a piezo method using mechanical vibration; a bubble jet (registered trademark) method that uses bubbles generated by heating, and the like. The ink jet recording method of the present invention can be used by any method.

The ink composition of the present invention has a clear magenta color, has high clarity of an image recorded on plain paper, inkjet dedicated paper, and the like, and has a hue suitable for the inkjet recording method. Further, the fastness of the recorded image, in particular, the water resistance is very high.
The ink composition of the present invention does not precipitate or separate pigment components during storage. Further, when the ink composition of the present invention is used for ink jet recording, crystal precipitation due to drying of the ink composition in the vicinity of the nozzle is very unlikely to occur, and the ejector (ink head) is not blocked. The ink composition of the present invention uses a continuous ink jet printer and has physical properties even when the ink is recirculated at a relatively long time interval or used intermittently by an on-demand ink jet printer. Does not change.

 Hereinafter, the present invention will be described specifically by way of examples. In the text, “parts” and “%” are based on weight unless otherwise specified. In addition, operations such as synthesis reaction and salting out were performed with stirring unless otherwise specified.

Example 1
(1)
N, N- dimethylformamide in 450 parts of the compound of formula _{(12) (R = CH 3} ) 51.0 parts, 23.9 parts of sodium carbonate, 18.0 parts of cupric acetate monohydrate and 114.0 parts of 5-acetylamino-2-sulfoaniline was added at room temperature, the temperature was raised to 130 to 135 ° C., and the reaction was carried out for 3 hours. The reaction was cooled to 20 ° C. and stirred for 30 minutes. The precipitated solid was collected by filtration, washed with 300 parts of methanol, and dried to obtain 62.9 parts of a compound of the above formula (13) in which R is methyl, as red crystals.
(2)
To 471 parts of water, 513 parts of 96% sulfuric acid was added dropwise under cooling to prepare 50% sulfuric acid, and the compound 61.3 of the formula (13) in which R obtained in Example 1 (1) is represented by methyl Parts were added. The reaction was heated to 123 ° C. and refluxed for 3 hours. The reaction solution was cooled with water, cooled to about 25 ° C., and stirred for 1 hour. The precipitated solid was collected by filtration and washed with 120 parts of water to obtain a red wet cake. The obtained wet cake was gradually added to a mixed solution of 2000 parts of water and 80 parts of a 25% aqueous sodium hydroxide solution. The mixture was stirred at room temperature for 1 hour, and the reaction solution was filtered to remove insolubles. After adding 100 parts of sodium chloride to the mother liquor and stirring for 1 hour at room temperature, the precipitated solid was collected by filtration and dried to convert 50.2 parts of the compound of the above formula (11) in which R is methyl into red. Obtained as crystals.
(3)
After adding 0.3 part of Leocoal TD-50 (manufactured by Lion Corporation, nonionic surfactant) to 120 parts of ice water to make a solution, 7.7 parts of cyanuric chloride was added and stirred for 30 minutes. Next, 8.3 parts of 5-amino-isophthalic acid sodium salt (purity 91.3%) is added, and a 25% aqueous sodium hydroxide solution is added dropwise at a temperature of 20 ° C. to adjust the pH in the reaction system to 3 to 3. 4 and a condensation reaction was carried out for 2 hours.
14.1 parts of the compound of the formula (11) in which R obtained in Example 1 (2) is represented by methyl is added to the obtained reaction solution, and the temperature is raised to 55-60 ° C., and 25% hydroxylation is performed. By dropping the aqueous sodium solution, the reaction system was kept at a pH of 5.3 to 5.7 and reacted for 1 hour. The solid precipitated from the reaction solution was collected by filtration and washed with 50 parts of water to obtain 126 parts of a wet cake containing a compound represented by the following formula (14).

(4)
In 600 parts of hot water, 126 parts of the wet cake obtained in Example 1 (3) was added, and an aqueous solution comprising 3.8 parts of 4,4′-diaminodicyclohexylmethane, 30 parts of water and 3.8 parts of 35% hydrochloric acid. And a 25% aqueous sodium hydroxide solution was added dropwise at 85 ° C. to maintain the pH in the reaction system at 9.0, and the reaction was carried out for 2 hours. Further, an aqueous solution composed of 1.2 parts of 4,4′-diaminodicyclohexylmethane, 10 parts of water and 1.2 parts of 35% hydrochloric acid was added, and the reaction was performed in the same manner for 2 hours to complete the reaction. The reaction solution was filtered to remove insoluble matters, warm water was added to adjust the amount of the mother liquor to 800 parts, concentrated hydrochloric acid was added at 60 to 65 ° C., and the pH was adjusted to 2. After 1 hour, crystals precipitated from the mother liquor were collected by filtration and washed with 1000 parts of hot water at about 60 ° C. to obtain the compound of the above formula (9) as a red wet cake.

(5)
The wet cake obtained in Example 1 (4) was added to 600 parts of methanol and heated to 60 to 65 ° C. After 1 hour, the precipitated solid was collected by filtration, washed with methanol, and dried to convert 25.0 parts of the purified compound of formula (9) having an inorganic impurity content of 1% by weight or less into red crystals. Got as.
λmax: 527 nm (in aqueous ammonia)

Example 2
(A) Preparation of ink The ink composition of the present invention was prepared by mixing the compound of formula (9) obtained in Example 1 (5) above and other ink preparation agents at the composition ratio shown in Table 2 below. I got a thing. The obtained ink composition was filtered through a 0.45 μm membrane filter to remove impurities. The water was ion-exchanged water, adjusted with ammonia water so that the pH of the ink composition was about 9.0, and then added so that the total amount was 100 parts.

Table 2 (Composition ratio of ink composition)
Compound of formula (9) obtained in Example 1 (5) 4.0 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butylcarbitol 2.0 parts Product name Surfynol 104PG50 (Note) 0.1 parts Ammonia water + water 76.9 parts Total 100.0 parts (Note) Acetylene glycol nonionic surfactant, manufactured by Nisshin Chemical Co., Ltd.

Comparative Example 1
In place of the compound of the above formula (9) obtained in Example 1 (5), No. 1 was given as a specific example of the dye of Patent Document 1. A comparative ink composition was prepared in the same manner as in Example 2 except that the dye described in 1 was used. The structural formula of the dye used is shown in the following formula (15). In addition, the ammonium salt was used for the compound of following formula (15).

Comparative Example 2
Example 2 except that the compound of the following formula (16) synthesized by the method described in Example 2 of Patent Document 2 is used instead of the compound of the above formula (9) obtained in Example 1 (5). Similarly, a comparative ink composition was prepared. The structural formula of the compound used is shown in the following formula (16). In addition, evaluation used the sodium salt of following formula (16).

(B) Inkjet printing Using an inkjet printer (trade name: PIXUS ip4100 manufactured by Canon Inc.), inkjet recording was performed on five types of plain paper shown in Table 3. During ink jet recording, a check pattern (a pattern in which 1.5 mm squares having a density of 100% and 0% were alternately combined) was created to obtain a magenta-white print with high contrast. The white portion is a portion of plain paper that is not colored with ink. In addition, an image pattern was prepared so that gradations with several reflection densities could be obtained, and a printed matter having a magenta gradation was obtained.
When performing a visual judgment in the water resistance test, a check pattern print was used.
The dye residual ratio measurement in the water resistance test was performed using a printed matter having gradation, and the reflection density was measured for a portion where the reflection density D value of the printed matter before the test was closest to 1. The reflection density was measured using a colorimetric system (product name: SpectroEye, manufactured by GretagMacbeth).
Various test methods for recorded images and evaluation methods for test results are described below.

Table 3
Plain paper 1
Product name LBP PAPER LS-500 manufactured by Canon Inc.
Plain paper 2
Product name Multipurpose Paper made by Hewlett Packard
Plain paper 3
Product name All-in-One Printing Paper made by Hewlett Packard
Plain paper 4
Seiko Epson double-sided high-quality plain paper KA4250NPD
Plain paper 5
Canon plain color paper LC-301

(C) Measurement of L *, a *, b * of printed matter L *, a *, b * values are measured using the above colorimetric system for the portion with the highest reflection density in the printed matter with printed gradation. did.
The results of Example 2 are shown in Table 4, the results of Comparative Example 1 are shown in Table 5, and the results of Comparative Example 2 are shown in Table 6, respectively. As for the hue by visual observation, both Example 2 and each Comparative Example showed a clear magenta color and were good.

Table 4
Example 2
L * a * b *
Plain paper 1 54.9 54.3 -5.4
Plain paper 2 56.6 53.0 -9.0
Plain paper 3 55.9 54.4 -9.2
Plain paper 4 57.6 50.1 -9.5
Plain paper 5 54.2 60.5 -6.8

Table 5
Comparative Example 1
L * a * b *
Plain paper 1 47.2 66.2 -1.4
Plain paper 2 47.6 64.3 -4.7
Plain paper 3 48.1 64.0 -4.7
Plain paper 4 48.5 62.3 -8.0
Plain paper 5 47.2 72.8 -2.2

Table 6
Comparative Example 2
L * a * b *
Plain paper 1 55.0 56.9 -7.0
Plain paper 2 56.5 55.5 -9.5
Plain paper 3 57.0 54.4-10.3
Plain paper 4 57.3 51.6 -10.
Plain paper 5 54.8 61.6 -8.1

(D) Water resistance test 1 (evaporation drying test)
One drop of ion-exchanged water was dropped on the check pattern printed matter that had been dried for 24 hours after printing, and then naturally dried. After drying, the degree of pattern bleeding was visually evaluated and evaluated in three stages according to the following criteria.
There is no bleeding at all (it cannot be determined where it was dripped).
There is almost no bleeding (the place where it was dripped can be identified) .... △
Obviously blurred ...
The results are shown in Table 7.

(E) Water resistance test 2 (immersion test 1)
A check pattern printed matter dried for 24 hours after printing was immersed in ion-exchanged water for 1 hour. After drying, the degree of color fading of the colored part of the pattern and the degree of coloring of the white part were visually evaluated and evaluated in three stages according to the following criteria.
There is no fading or coloring at all ...
Some color fading and coloring can be seen ...
Clearly discoloration and coloring can be seen ...
The results are shown in Table 8.

(F) Water resistance test 3 (immersion test 2)
The gradation printed matter dried for 24 hours after printing was immersed in ion-exchanged water for 1 hour. After drying, the reflection density was measured using the color measurement system. After the measurement, the dye residual ratio was calculated by (reflected density after test / reflected density before test) × 100 (%), and evaluated in three stages according to the following criteria.
Dye residual ratio is 90% or more ...
Dye residual ratio is 50% or more and less than 90% ... △
Dye remaining rate is less than 50% ...
The results are shown in Table 9.

Table 7 Results of water resistance test 1

Plain paper 1 Plain paper 2 Plain paper 3 Plain paper 4 Plain paper 5
Example 2 △ ○ ○ ○ ○
Comparative Example 1 × × × × △
Comparative Example 2 × × × × △

Table 8 Results of water resistance test 2

Plain paper 1 Plain paper 2 Plain paper 3 Plain paper 4 Plain paper 5
Example 2 ○ ○ ○ ○ ○
Comparative Example 1 × × × × △
Comparative Example 2 × × × × △

Table 9 Results of water resistance test 3

Plain paper 1 Plain paper 2 Plain paper 3 Plain paper 4 Plain paper 5
Example 2 ○ ○ ○ ○ ○
Comparative Example 1 × × × × ○
Comparative Example 2 × × × △ ○

As is clear from the results in Tables 7 to 9, the images of the comparative examples recorded on the plain paper 5 are equivalent to the respective examples in the water resistance test 3, and each of the examples in the water resistance tests 1 and 2 also. It was slightly inferior. Therefore, only when the plain paper 5 is used, it can be said that the water resistance of each comparative example is not so bad. In Comparative Example 2, the same level of water resistance was exhibited when plain paper 4 was used.
However, in the plain papers 1 to 3, a clear difference was recognized between each example and each comparative example. In other words, the recorded images of each example with respect to each comparative example showed extremely excellent water resistance in both visual and colorimetric results, and the usefulness of the dye of the present invention and the ink containing the same was clear. It became.

  From the above results, the water-soluble anthrapyridone compound of the present invention is suitable for preparing an ink composition for inkjet recording, and is excellent in various fastness properties, particularly water resistance, and has high water solubility and good With a clear hue. From these characteristics, it is apparent that the anthrapyridone compound of the present invention is a very useful compound as various recording ink dyes, particularly as magenta dyes for inkjet inks.

Claims (16)

Anthrapyridone compound represented by the following formula (1) or a salt thereof

(In the formula, R represents a hydrogen atom or an alkyl group, Y represents a mono- or dicarboxy-substituted anilino group, and X represents a bridging group.) R is a hydrogen atom or a C1-C4 alkyl group,
The anthrapyridone compound according to claim 1, wherein Y is a mono- or dicarboxy-substituted anilino group, and the bridging group X is N, N-hydrazinediyl or a group selected from the following formulas (2) to (8): salt

(In the formula (2), n is 2 to 8)

(In formula (3), R ² represents a hydrogen atom or a methyl group)

(In formula (6), m represents 2 to 4)

R is a methyl group,
Y is a 3,5-dicarboxyanilino group or a 2,5-dicarboxyanilino group,
Formula (2) in which the bridging group X is N, N′-hydrazinediyl; n is represented by 2 to 6; Formula (3) in which R ² is a hydrogen atom or a methyl group; Formula (4); Formula (5) An anthrapyridone compound or a salt thereof according to claim 1 or 2, which is a group selected from the formula (6); the formula (7); or the formula (8), wherein m is 3. R is a methyl group,
Y is a 3,5-dicarboxyanilino group;
The bridging group X is a formula (2) in which n is represented by 2 to 6; or a formula (3) in which R ² is a hydrogen atom or a methyl group. An anthrapyridone compound or a salt thereof according to The anthrapyridone compound or a salt thereof according to any one of claims 1 to 4 represented by the following formula (9):

An ink composition comprising the anthrapyridone compound or a salt thereof according to any one of claims 1 to 5. The ink composition according to claim 6, comprising water and a water-soluble organic solvent. The ink composition according to claim 7, which is for ink jet recording. The ink composition according to any one of claims 6 to 8, wherein the content of inorganic impurities in the total amount of the anthrapyridone compound according to any one of claims 1 to 5 is 1% by weight or less. The ink composition according to any one of claims 6 to 9, wherein the content of the anthrapyridone compound according to any one of claims 1 to 5 is 0.1 to 20% by weight or less. 11. An ink jet recording method for recording on a recording material by ejecting ink droplets according to a recording signal, wherein the ink composition according to any one of claims 6 to 10 is used as an ink. Method The inkjet recording method according to claim 11, wherein the recording material is an information transmission sheet. The inkjet recording method according to claim 12, wherein the information transmission sheet contains an ink image-receiving layer containing plain paper or a porous white inorganic substance. A colored body colored with the ink composition according to any one of claims 6 to 10. The colored body according to claim 14, wherein the coloring is performed by an ink jet printer. An inkjet printer filled with a container containing the ink composition according to any one of claims 6 to 10.