JP2012149118A - Ink composition, coloring material or salt thereof, inkjet recording method, and colored body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition containing a magenta coloring material providing recorded images excellent in light resistance and ozone resistance, particularly the ink composition for inkjet recording.SOLUTION: The ink composition for inkjet recording contains at least one compound represented by formula (13) or the salt thereof as a coloring material, and includes an antiseptic and mildewproofing agent, pH adjuster, chelate reagent, corrosion inhibitor, water-soluble ultraviolet absorbent, water-soluble polymer compound, dye-solubilizer, surfactant or the like to provide a recorded image excellent in light resistance and ozone resistance.

Description

The present invention relates to an ink composition, a compound contained in the ink composition as a pigment or a salt thereof, an ink jet recording method, and a colored body colored by these.

Among various color recording methods, a water-based ink in which a water-soluble dye is dissolved in an aqueous medium is used as one of the ink-jet recording methods, that is, one of the representative methods. Yes. The performance required for water-based inks is to provide a recording image with sufficient density; no clogging of the discharge nozzles; good dryness on the recording material; little bleeding; It must be excellent. In addition, in order to reproduce the image or character information on the color display of a computer in full color as faithfully as possible, each of the yellow (Y), magenta (M), and cyan (C) inks used for ink-jet recording is as much as possible. It is desirable to have a hue close to that of the standard and to be clear. Further, images obtained by inkjet recording are required to have image fastness such as water resistance, moisture resistance, light resistance and gas resistance (including SOx, NOx, especially ozone gas). Among these, the technology for greatly improving the light resistance has not been established yet, and among the four primary colors Y, M, C, and black (K) used as necessary, the recorded image of magenta is light resistant. Since many of them are weak, improvement is one of the important issues.

A typical magenta dye used in the aqueous inkjet ink is an azo dye using xanthene dye and 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid. However, the former is extremely excellent in hue and sharpness but very inferior in light resistance. The latter is good in terms of hue and water resistance, but is inferior in light resistance and ozone gas resistance. Also, for the purpose of improving light resistance, metal complexes of azo dyes have been proposed, but the sharpness and ozone gas resistance are extremely poor.

Examples of magenta dyes that are excellent in sharpness, oxidation resistance gas resistance and light resistance include anthrapyridone dyes (for example, see Patent Documents 1 to 13). However, none satisfying all of the hue, sharpness, light resistance, water resistance, oxidation resistance gas resistance, and storage stability of the ink (composition) containing the coloring matter has yet been obtained.
Patent Documents 9, 12 and 13 disclose a magenta dye having a structure in which two molecules of an anthrapyridone compound are crosslinked by a crosslinking group, and an ink composition containing the dye.

JP-A-10-306221 JP 2000-109464 A JP 2000-169776 A JP 2000-191660 A Japanese Patent Laid-Open No. 2000-256587 JP 2001-72884 A Japanese Patent Laid-Open No. 2001-139836 International Publication No. 2004/104108 Pamphlet JP 2003-192930 A Japanese Patent Laying-Open No. 2005-8868 JP 2005-314514 A International Publication 2006/0775706 Pamphlet International Publication No. 2008/066062 Pamphlet International Publication No. 2009/093433 Pamphlet JP 2010-059217 A International Publication No. 2007/018175 Pamphlet

An object of the present invention is to provide an ink composition containing a magenta dye, particularly an ink composition for inkjet recording, which gives a recorded image excellent in light resistance and ozone resistance (durability against ozone gas).

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an ink composition containing a compound represented by the specific formula (1) as a pigment solves the above-mentioned problems. It has been completed.
That is, the present invention relates to the following 1) to 12).

1)
An ink composition containing at least one compound represented by the following formula (1) or a salt thereof as a pigment;

[In Formula (1),
R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, and R ¹ and R ² may combine to form a cycloalkylene ring together with the two carbon atoms that they substitute,
Group A represents a group represented by the following formula (2),
The group B represents a carboxy group or a group represented by the following formula (2). ],

[In Formula (2),
* Represents the binding site as group A;
n represents an integer of 0 or 1,
R ³ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, or a cyanoalkyl group,
R ⁴ represents a hydrogen atom, a halogen atom, a carboxy group, an alkyl group, an alkoxy group, or a sulfo-substituted phenyl group. ].
2)
In equation (1),
R ¹ and R ² are each independently a hydrogen atom or a C1-C6 alkyl group,
R ¹ and R ² may combine to form a C5-C10 cycloalkylene ring with the two carbon atoms that each substitutes;
Group A is a group represented by Formula (2),
Group B is a carboxy group or a group represented by formula (2);
In equation (2),
* Is the binding site as group A;
n is an integer of 0 or 1,
R ³ is a hydrogen atom, a C1-C6 alkyl group, a hydroxy C1-C6 alkyl group, a cyclohexyl group, or a cyano C1-C6 alkyl group,
The ink composition according to 1), wherein R ⁴ is a hydrogen atom, a halogen atom, a carboxy group, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a sulfo-substituted phenyl group.
3)
In equation (2),
R ³ is a hydrogen atom or a C1-C6 alkyl group,
The ink composition according to 1) or 2), wherein R ⁴ is a hydrogen atom, a C1-C6 alkyl group, or a sulfo-substituted phenyl group.
4)
The ink composition according to any one of 1) to 3), further including a water-soluble organic solvent.
5)
The ink composition according to any one of 1) to 4), which is used for inkjet recording.
6)
An ink jet recording method for performing recording by ejecting the droplets of the ink composition according to any one of 1) to 5) according to a recording signal to adhere to a recording material.
7)
6. The inkjet recording method according to 6) above, wherein the recording material is an information transmission sheet.
8)
The ink jet recording method according to 7), wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance.
9)
A colored body colored with the ink composition according to any one of 1) to 5).
10)
A colored product colored by the inkjet recording method described in 6) above.
11)
The inkjet printer with which the container containing the ink composition as described in any one of said 1) thru | or 5 was loaded.
12)
A compound represented by the following formula (1) or a salt thereof,

[In Formula (1),
R ¹ and R ² each independently represents a hydrogen atom or an alkyl group,
R ¹ and R ² may combine to form a cycloalkylene ring with the two carbon atoms that they each replace,
The group A is a group represented by the following formula (2), and the group B represents a carboxy group or a group represented by the following formula (2). ],

[In Formula (2),
* Represents the binding site as group A;
n represents an integer of 0 or 1,
R ³ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, or a cyanoalkyl group,
R ⁴ represents a hydrogen atom, a halogen atom, a carboxy group, an alkyl group, an alkoxy group, or a sulfo-substituted phenyl group. ].

According to the present invention, it was possible to provide a magenta dye and an ink composition containing the same, particularly an ink composition for inkjet recording, which gives a recorded image excellent in light resistance and ozone resistance.

The present invention will be described in detail.
In the present specification, unless otherwise specified, in order to avoid complications, both (anthrapyridone) “compounds or salts thereof” of the present invention are simply simplified as “anthrapyridone” “compounds” of the present invention. In the following, it means both “compound or salt thereof”.

The ink composition of the present invention is a substantially aqueous ink composition containing at least one compound of the present invention represented by the formula (1) as a pigment. It describes about the compound represented by this Formula (1).

In the formula (1), examples of the alkyl group for R ¹ and R ² include linear or branched ones. The range of carbon number is usually C1-C6, preferably C1-C4, more preferably C1-C3, and still more preferably C1 or C2.
Specific examples thereof include straight chain such as methyl, ethyl, n-propyl, n-butyl and n-pentyl; branched chain such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl and tert-pentyl. Thing; etc. are mentioned. Of these, methyl and ethyl are preferred.

When R ¹ and R ² are combined to form a cycloalkylene ring with two carbon atoms each substituting, the carbon number range of the cycloalkylene ring is usually C5-C10, preferably C5-C8, More preferred is C5 or C6, and particularly preferred is C6. Specific examples thereof include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, cyclohexylene is preferred.

Among the above, preferable R ¹ and R ² include a hydrogen atom, a C1-C6 alkyl group (preferably a methyl group), or a cyclohexylene ring formed with two carbon atoms substituted by R ¹ and R ² respectively. , Each independently preferably a hydrogen atom or a C1-C6 alkyl group, particularly preferably both are hydrogen atoms.

The group A in the formula (1) represents a group represented by the formula (2).
In the formula (2), the carbon atom indicated by “*” represents a binding site as the group A. That is, in the group represented by the formula (2), the carbon atom indicated by “*” in the formula is bonded to one nitrogen atom in the formula (1) via a methylene group.

In formula (2), n means the number of sulfo groups whose substitution positions are not specified, and represents an integer of 0 or 1. n is preferably 1.

In formula (2), examples of the alkyl group for R ³ include straight-chain, branched-chain, or cyclic groups, with straight-chain or cyclic groups being preferred, and straight-chain groups being more preferred. The range of carbon number is usually C1-C6, preferably C1-C5, more preferably C1-C4. However, for a branched chain or cyclic group, a range of C3-C6 carbon number is preferably mentioned. Specific examples include straight chain such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl; branched such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl and tert-pentyl. A chain; a cyclic group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; and the like. Among these, methyl, ethyl, and cyclohexyl are preferable, methyl or cyclohexyl is more preferable, and methyl is particularly preferable.

Examples of the hydroxyalkyl group in R ³ include those in which any carbon atom of the “alkyl group in R ³ ” is substituted with a hydroxy group. However, those in which both the hydroxy group and the nitrogen atom are not substituted on the same carbon atom are preferred.
The alkyl moiety in the hydroxyalkyl group is preferably linear or branched, and more preferably linear. The range of the carbon number of the alkyl moiety is usually C1-C6, preferably C1-C5, more preferably C1-C4.
Specific examples include straight-chain C1-C6 alkyl moieties such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, etc .; 1-hydroxy-2-propyl, C1-C6 alkyl moieties such as 1-hydroxy-2-butyl, 1-hydroxy-3-butyl, 2-hydroxy-3-pentyl, 2-hydroxy-1,1-dimethylethyl, etc. are branched; It is done. In these, 2-hydroxyethyl is mentioned preferably.

Examples of the cyanoalkyl group in R ³ include the same as the “hydroxyalkyl group in R ³ ” except that “hydroxy” is replaced with “cyano”, and the range of carbon number and the like may be the same. Specific examples include straight-chain C1-C6 alkyl moieties such as 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 3-cyanobutyl, 4-cyanobutyl; 1-cyano-2-propyl, 1-cyano C1-C6 alkyl moieties such as 2-butyl, 1-cyano-3-butyl, 2-cyano-3-pentyl, 2-cyano-1,1-dimethylethyl, etc. are branched; Of these, 2-cyanoethyl is preferred.

Among these, preferable R ³ includes a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

In formula (2), examples of the halogen atom for R ⁴ include a fluorine atom, a chlorine atom, and a bromine atom, with a chlorine atom being preferred.

As the alkyl group for R ^4, the same groups as those described above for “alkyl group for R ¹ and R ² ”, including preferable ones, and the like can be mentioned.

Examples of the alkoxy group for R ⁴ include straight-chain or branched-chain groups, and straight-chain groups are preferred. The range of carbon number is usually C1-C6, preferably C1-C4. However, in the case of a branched chain, the range of carbon number is usually C3-C6, preferably C3-C4. Specific examples thereof include a straight chain such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy; isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, tert-pentoxy, tert -Branched chain such as hexyloxy; and the like. Of these, methoxy and ethoxy are preferred.

The sulfo-substituted phenyl group for R ⁴ includes a phenyl group substituted with one or two sulfo groups, and the former is preferable. Specific examples thereof include those substituted with one sulfo group such as 2-sulfophenyl, 3-sulfophenyl and 4-sulfophenyl; two such as 2,4-disulfophenyl and 3,5-disulfophenyl. And the like substituted with a sulfo group. Of these, 4-sulfophenyl is particularly preferred.

Among the above, preferable R ⁴ includes a hydrogen atom, an alkyl group (preferably a C1-C6 alkyl group), or a sulfo-substituted phenyl group.

In the formula (1), the group B represents a carboxy group or a group represented by the formula (2), and both are preferable.
Further, when the group B is a group represented by the formula (2), the group A and the group B may be a group represented by the same formula (2), or each independently represented by a different formula (2). It may be a group. When the group A and the group B are both groups represented by the formula (2), it is preferable that both are the same.

In formula (2), the “— (SO ₃ H) n” group whose substitution position is not specified and the substitution position of R ⁴ are not particularly limited, but the following combinations i) to iii) are preferable.
In addition, about a substituted position, the bond position of the oxygen atom couple | bonded with the benzene ring which these groups substitute is described as 1st position.
i)
When R ⁴ is a hydrogen atom, n is an integer of 1 and the substitution position of the “— (SO ₃ H) n” group is the 4th position.
ii)
When R ⁴ is other than a hydrogen atom (preferably an alkyl group or a sulfo-substituted phenyl group), n is an integer of 1 and the substitution position of the “— (SO ₃ H) n” group is the 2-position or the 3-position.
iii)
When n is 0 and R ⁴ is other than a hydrogen atom (preferably a carboxy group), the substitution position of R ⁴ is the 3rd position.
Among these, the combination of i) or ii) is more preferable.

Group A in Formula (1) and (2), group B, R ¹ to R ^4, n, R ⁴ and - the substitution position of "(SO ₃ H) n" group, compounds in combination with each other be preferred More preferred is a combination of more preferred ones. The same applies to combinations of preferable and more preferable ones.

The salt of the compound of the formula (1) is a salt formed with an inorganic or organic cation.
Preferred examples of the salt formed with the inorganic cation include alkali metal salts such as lithium salts, sodium salts, potassium salts; or ammonium (NH ₄ ⁺ ) salts.
Preferred examples of the salt formed with the organic cation include a salt formed with quaternary ammonium represented by the following formula (3).

[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 Z ^{1 to} Z ⁴ is a group other than a hydrogen atom. It is. ]

In formula (3), specific examples of Z ^{1 to} Z ⁴ include C1-C6 alkyl groups (preferably C1-C4 alkyl groups) such as methyl, ethyl, and butyl; hydroxymethyl, 2-hydroxyethyl, 3-hydroxy Hydroxy C1-C6 alkyl groups (preferably hydroxy C1-C4 alkyl groups) such as propyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl; hydroxyethoxymethyl, 2-hydroxyethoxyethyl, And hydroxy C1-C6 alkoxy C1-C6 alkyl groups (preferably hydroxy C1-C4 alkoxy C1-C4 alkyl groups) such as 3-hydroxyethoxypropyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, and the like.

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

The salt of the compound represented by the formula (1) may be any of a single salt, a plurality of kinds of mixed salts, or a mixture of a free acid and a salt. The compound represented by the formula (1) may vary in physical properties such as solubility, or the performance of ink containing the compound, particularly in terms of fastness, depending on the type of salt. For this reason, it is also preferable to select the type of salt according to the performance of the target ink.
Methods for producing various salts from free acids; methods for obtaining free acids from various salts; methods for exchanging salts from specific salts to other salts; Can be used.

Specific examples of the compound represented by the formula (1) of the present invention are shown in the following Tables 1 and 2, but the present invention is not limited to these specific examples.
“Position of — (SO ₃ H) n group” and “position of R ⁴ ” in each table mean the substitution positions of these groups.
However, when n is 0 and R ⁴ is a hydrogen atom, the substitution position is not described, and the symbol “-” is described.
Further, in each table, “c-Hexl” described across R ¹ and R ² is the same as the formula (1) in which R ¹ and R ² are bonded to each other, together with the two carbon atoms that are substituted. It means the formed cyclohexylene ring.
The symbols in other tables have the following meanings.
Me: methyl group.
MeO: methoxy group.
4-S-Ph: 4-sulfophenyl group.

The production method of the compound of the present invention is described below. The groups A, B, R ^{1 to} R ⁴ , and n described in the following formulas (5) to (7) have the same meanings as in the formulas (1) and (2). The number of moles of the compound described in the production method is a representative example, and those skilled in the art can understand that the number can be appropriately increased or decreased as necessary.
The compound of the present invention is produced, for example, by the following method. That is, a compound represented by the following formula (5) can be obtained by synthesis according to a known method described in WO2007-018175 or the like, or according to the method.

To 1 mol of the obtained compound of the formula (5), an anionic and / or cation exchange resin; an aqueous sodium hydroxide solution; 0.5 mol of a compound of the following formula (6) in a solvent such as ethanol, ethylene glycol, or other alcohols or polyols; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, or other amides; And 30 to 100 ° C. to obtain a compound of the following formula (7). The aqueous solution containing the compound of formula (5) after neutralization may be used as it is, but it is preferable to use it for the next reaction after drying to obtain a solid containing the compound of formula (5). Further, as the solvent, it is preferable to use an aprotic solvent (preferably an aprotic polar solvent such as an amide).

Next, 1 mol of the obtained compound of the formula (7) and 1 mol of a copper compound such as copper acetate, copper sulfate, copper halide (eg, copper chloride, copper iodide, etc.), water; methanol, ethanol, ethylene Alcohol and polyols such as glycol; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; Of the formula (1).
Any base can be used to adjust the pH in this reaction, but alkali metal carbonates (eg, lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkali metal hydroxides (eg, lithium hydroxide, hydroxide) Sodium, potassium hydroxide, etc.) are preferred.

  The compound represented by the formula (1) is an inorganic impurity such as a metal cation chloride (such as sodium chloride) and a sulfate (such as sodium sulfate) contained as an impurity in the total mass of the compound. It is preferable to use a small amount. The standard of the content is, for example, about 1% by mass or less. Examples of the method for producing the compound of the present invention with a small amount of inorganic impurities include a known method using a reverse osmosis membrane; a method for suspension purification using C1-C4 alcohol (or the alcohol containing water depending on the case), etc .; or Examples include a known method using an anion and a cation exchange resin as appropriate;

The ink composition of the present invention is obtained by dissolving the compound represented by the formula (1) as a pigment component and water or an aqueous solvent (water containing a water-soluble organic solvent described later). In the ink composition of the present invention, for example, the reaction liquid after completion of the final step in the step of synthesizing the compound represented by the formula (1) can be directly used for the production of the ink composition. In addition, the target product can be isolated from the reaction solution by, for example, crystallization; or spray drying; and the like, dried, and then used in the ink composition.
The ink composition of the present invention usually contains 0.1 to 20% by mass, preferably 1 to 15% by mass, and more preferably 2 to 10% by mass of the compound represented by the formula (1). The ink composition of the present invention may contain a water-soluble organic solvent in an amount of 0 to 30% by mass, preferably 5 to 20% by mass; and an ink preparation agent in an amount of 0 to 10% by mass. The water-soluble organic solvent is used in view of the effects of dissolution of the dye, prevention of drying, adjustment of viscosity, promotion of penetration, adjustment of surface tension, defoaming and the like, and it is preferably contained in the ink composition.

The ink composition of the present invention is a composition containing at least one compound represented by the formula (1), and the type and number of the compound are not particularly limited. For example, a plurality of compounds may be blended for the purpose of (finely) adjusting the hue, print density, etc. of the ink composition to a desired one.
As an example, a compound in which the group B in the formula (1) is a group represented by the formula (2) and a compound that is a carboxy group may be blended, and the blending ratio of both compounds is not particularly limited. Considering the print density and various image fastnesses, as a guideline for blending both, the area ratio of HPLC is the former / the latter ratio rounded off to the first decimal place, usually 1/99 ~ 99/1, preferably 1/10 to 10/1, more preferably 1/10 to 9/1, still more preferably 1/10 to 8/1, particularly preferably 1/10 to 7/1, and in some cases A blending ratio of 1/10 to 6/1 is mentioned. The detection wavelength used when calculating the HPLC area ratio is preferably 254 nm.

Examples of water-soluble organic solvents that can be used in the ink composition of the present invention include C1-C4 alkanols (alcohols) such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol. ); Carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethyl Heterocyclic ureas such as hexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol, 1,2- or 1,3-propylene rubber C2-C6 such as coal, 1,2- or 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol Mono, oligo or polyalkylene glycol or thioglycol having an alkylene unit; polyol (triol) such as glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether or triethylene Recall C1-C4 alkyl ethers of polyhydric alcohols monoethyl ether; .gamma.-butyrolactone; or dimethyl sulfoxide and the like.

Among these, preferred are isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, diethylene glycol monobutyl ether, more preferably isopropanol, glycerin, Examples include diethylene glycol monobutyl ether (butyl carbitol), 2-pyrrolidone, and N-methyl-2-pyrrolidone.
These water-soluble organic solvents are used alone or in combination.

Hereinafter, ink preparation agents that can be used for preparing the ink composition of the present invention will be described. Examples of the ink preparation agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye dissolving agents, and surfactants.

Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, Benzothiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And benzyl bromacetate compounds.
An example of the organic halogen compound is sodium pentachlorophenol.
Examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide.
Examples of the isothiazoline-based compound include 1,2-benzisothiazoline-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 and antifungal agents include sodium sorbate, sodium benzoate, anhydrous sodium acetate, and Avecia, trade names: Proxel ^RTM GXL (S), Proxel ^RTM XL-2 (S), and the like.
In the present specification, the superscript “RTM” means a registered trademark.

As the pH adjuster, any substance can be used as long as it can control the pH of the ink in the range of 7.5 to 11.0 without adversely affecting the prepared ink. For example, alkanolamines such as diethanolamine and triethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water); or lithium carbonate, sodium carbonate and potassium carbonate And alkali metal carbonates.

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

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

Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone 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 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 salts thereof, N-acyl methyl taurate, alkyl sulfate 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, alkylaryl sulfonate, diethylsulfate , Diethylhexylsylsulfosuccinate, dioctylsulfosuccinate and the like.

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

Examples of 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 Etc.

Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl -1-hexyne-3-acetylene alcohol such as ol; As another example, manufactured by Nissin Chemical Industry Co., Ltd., trade name Surfynol ^RTM 104E, the 104PG50, 82, 465, trade name Olfine ^RTM STG and the like; Etc. These ink preparation agents are used alone or in combination.

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

In the method for producing the ink composition of the present invention, the order in which the components are dissolved is not particularly limited. The compound of the present invention may be dissolved in water or the aqueous solvent in advance, and the ink preparation agent may be added, or the water-soluble organic solvent and the ink preparation agent may be added after dissolving the compound in water. . The order may be different from this. Furthermore, a reaction solution after completion of the final step in the synthesis reaction of the compound of the present invention; or an aqueous solution obtained by subjecting the compound of the present invention to a desalting treatment with a reverse osmosis membrane; An ink composition may be produced by adding an ink preparation agent or the like.
The water used for preparing the ink composition is preferably water with few impurities such as ion exchange water or distilled water. The ink composition thus prepared may be subjected to microfiltration using a membrane filter or the like as necessary to remove impurities. When the ink composition is used for inkjet recording, microfiltration is preferably performed. The pore diameter of the filter for performing microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

In the ink jet recording method of the present invention, a container containing the ink composition of the present invention is loaded in a predetermined position of an ink jet printer, and (small) droplets of the ink composition are ejected according to a recording signal to be recorded. This is a method for recording on a material. In the inkjet recording method of the present invention, the ink composition of the present invention can be used alone as a magenta ink. For example, each color such as yellow, cyan, green, orange, blue (or violet), and black as necessary A full color recorded image can also be obtained by using together with the ink composition. At this time, containers containing ink compositions appropriately selected from the above-described colors may be loaded and used at predetermined positions of the ink jet printer.
Examples of the discharge method 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 ink composition of the present invention can be used in any of these ejection methods.

Examples of the recording material to which the ink jet recording method of the present invention can be applied include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and color filter base materials. Can be mentioned.
As the information transmission sheet, a surface-treated sheet, specifically, a substrate (for example, the above-mentioned recording material) provided with an ink receiving layer is preferable. For example, the ink-receiving layer may be impregnated or coated with a cationic polymer on a base material; porous silica, alumina sol, special ceramics, or other porous white inorganic substances capable of adsorbing pigments in ink, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Coating on the surface of the substrate together with the hydrophilic polymer. A paper provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film) or the like. Commercially available products include, for example, manufactured by Pictorico Co., Ltd., trade name Pictorico ^RTM Pro; manufactured by Canon Inc., trade name Professional Photo Paper, Super Photo Paper, Matt Photo Paper; manufactured by Epson Corp., trade name Krispia ^RTM , photographic paper ( Glossy), photo matte paper, Glossy film for Superfine; manufactured by Nippon Hewlett-Packard Co., Ltd., trade name Advanced Photo Paper, Premium Plus Photo Paper, Premium Glossy Film, Photo Paper; manufactured by Konica Minolta Photo Imaging Co., Ltd., trade name Photo-like QP;
Of course, an information transmission sheet having no ink receiving layer, such as plain paper such as PPC (plain paper copy) paper, can be used as a recording material.

Among these, it is known that discoloration due to ozone gas in an image recorded on a recording material coated with a porous white inorganic substance on the surface is particularly large. Since the water-based magenta ink composition of the present invention is excellent in resistance to ozone gas in addition to light resistance, it is particularly effective when recording on such a recording material.

Examples of the porous white inorganic substance 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.

The colored body of the present invention means a substance colored with the 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, the recording material described above.
Examples of the coloring method include a dip dyeing method, a textile printing method, a printing method such as screen printing, and an ink jet recording method. The colored body of the present invention is preferably a colored body colored by the inkjet recording method of the present invention.

  The ink composition of the present invention has a clear magenta color, has a clear hue particularly on glossy paper, and has high fastness of recorded images. Moreover, it is highly safe for humans.

The ink composition of the present invention can be used for various recording and printing applications such as printing, copying, marking, writing, drawing, stamping and the like, and is particularly suitably used as an ink for inkjet recording. The ink composition of the present invention can be used for recording on plain paper, but has a high print density of an image recorded on special inkjet paper or glossy paper, and has a hue suitable for inkjet recording.
Further, the recorded images have various fastnesses such as water resistance, light resistance, ozone resistance, friction resistance, and moisture resistance, in particular, light resistance and ozone resistance.
The ink composition of the present invention does not precipitate or separate during storage, and has extremely high storage stability. Further, since the compound of the present invention is excellent in water solubility, when the ink composition of the present invention containing the compound is used for ink jet recording, solid precipitation due to drying of the ink composition in the vicinity of the nozzle is very unlikely to occur. The container (ink head) is not blocked. The ink composition of the present invention has physical properties even in a use environment such as use under a constant recirculation for a relatively long time in a continuous ink jet printer; or intermittent use in an on-demand ink jet printer; Does not change.

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “parts” and “%” are based on mass unless otherwise specified. In addition, the operations such as each reaction and crystallization were performed under stirring unless otherwise specified.
Moreover, the maximum absorption wavelength ((lambda) max) of each compound or mixture in an Example described the measured value in the aqueous solution of pH 5-8 unless there is particular notice.
When the required amount of the target compound was not obtained by one synthesis reaction, the same synthesis reaction was repeated until the required amount was obtained.

[Example 1]
(Process 1)
75.4 parts of a wet cake containing a compound represented by the following formula (9) obtained by following the method described in Patent Document 4 was dissolved in 200 parts of ion-exchanged water, and 120 parts of anion exchange resin Diaion ^RTM SA10AOH. And 36 parts of cation exchange resin Diaion ^RTM SK1BH (both manufactured by Mitsubishi Chemical Corporation) were added as appropriate, and the mixture was stirred for 2 hours while maintaining the pH of the solution at 6.0 to 8.0. The ion exchange resin was removed from the resulting liquid by filtration, 500 parts of isopropyl alcohol was added, and the precipitated solid was collected by filtration and dried to obtain 38.9 parts of a compound represented by the following formula (9). It was.

(Process 2)
To 35 parts of N-methylpyrrolidone, 1.6 parts of the compound represented by the formula (9) obtained in Example 1 (Step 1) and 0.7 parts of ethylenediaminetetraacetic acid dianhydride are added, and the mixture is heated to 80 to 85 ° C. The mixture was heated for 4 hours. The obtained reaction solution was added to 400 parts of 2-propanol, and the precipitated solid was collected by filtration to obtain 3.5 parts of a wet cake containing the compounds represented by the following formulas (10) and (11). Obtained.

(Process 3)
3.5 parts of a wet cake containing the compounds represented by formula (10) and formula (11) obtained in Example 1 (step 2) is added to 100 parts of water, and the pH of the solution is 8.0 with sodium carbonate. Adjusted. To this solution, 0.6 parts of copper (II) acetate monohydrate was added, and the mixture was reacted at 25 to 30 ° C. for 2 hours while adjusting the pH to 6.5 to 7.5 using a 15% aqueous sodium carbonate solution. It was. 70 parts of methanol and 150 parts of isopropyl alcohol were added to the resulting reaction solution, and the precipitated solid was collected by filtration. The obtained solid was dissolved in 75 parts of water, 400 parts of 2-propanol was added, and the precipitated solid was collected by filtration and dried to obtain a compound represented by the following formulas (12) and (13). 0.8 parts of a red solid of the mixture were obtained. The HPLC area ratio of the compound represented by Formula (12) and Formula (13) in the obtained solid was 91/9.
λmax: 526 nm.

[Example 2]
(Process 1)
To 63 parts of N-methylpyrrolidone, 4.6 parts of the compound represented by the formula (9) obtained in Example 1 (Step 1) and 0.5 part of ethylenediaminetetraacetic acid dianhydride are added, and the mixture is heated to 80 to 85 ° C. The reaction was conducted by heating for 5 hours. The obtained reaction solution was added to 450 parts of 2-propanol, and the precipitated solid was collected by filtration to obtain 6.7 parts of a wet cake containing the compounds represented by the above formulas (10) and (11). Obtained.

(Process 2)
6.7 parts of a wet cake containing the compounds represented by formula (10) and formula (11) obtained in Example 2 (step 1) is added to 70 parts of water, and the pH of the solution is 8.0 with sodium carbonate. Adjusted. To this solution, 0.5 part of copper (II) acetate monohydrate was added, and the mixture was reacted at 25-30 ° C. for 2 hours while adjusting the pH to 6.5-7.5 using a 15% aqueous sodium carbonate solution. It was. 60 parts of methanol and 150 parts of isopropyl alcohol were added to the resulting reaction solution, and the precipitated solid was collected by filtration. The obtained solid was dissolved in 70 parts of water, 400 parts of 2-propanol was added, and the precipitated solid was collected by filtration and dried, whereby the compounds represented by the above formulas (12) and (13) were obtained. 3.9 parts of a red solid of the mixture was obtained. The HPLC area ratio of the compounds represented by formula (12) and formula (13) in the obtained solid was 17/83.
λmax: 525 nm.

[Example 3]
(Process 1)
To 65 parts of N, N-dimethylformamide is added 4.7 parts of the compound represented by the formula (9) obtained in Example 1 (Step 1) and 0.5 part of ethylenediaminetetraacetic acid dianhydride, and 85 to 90 parts. The mixture was heated to 0 ° C. and reacted for 8 hours. The obtained reaction liquid was added to 460 parts of 2-propanol, and the precipitated solid was collected by filtration to obtain 7.0 parts of a wet cake containing the compounds represented by the formulas (10) and (11). Obtained.

(Process 2)
7.0 parts of a wet cake containing the compound represented by formula (10) and formula (11) obtained in Example 3 (step 1) is added to 75 parts of water, and the pH of the solution is 8.0 with sodium carbonate. Adjusted. To this solution, 0.5 part of copper (II) acetate monohydrate was added, and the mixture was reacted at 25-30 ° C. for 2 hours while adjusting the pH to 6.5-7.5 using a 15% aqueous sodium carbonate solution. It was. 50 parts of methanol and 180 parts of isopropyl alcohol were added to the resulting reaction solution, and the precipitated solid was collected by filtration. The obtained solid was dissolved in 70 parts of water, 400 parts of 2-propanol was added, and the precipitated solid was collected by filtration and dried, whereby the compounds represented by the above formulas (12) and (13) were obtained. 3.5 parts of a red solid of the mixture were obtained. The HPLC area ratio of the compounds represented by the formula (12) and the formula (13) in the obtained solid was 14/86.
λmax: 526 nm.

[Example 4]
(Process 1)
In 300 parts of N, N-dimethylformamide, 95.3 parts of a compound represented by the following formula (14), 25.8 parts of phenol, and 20.0 parts of potassium carbonate were added and reacted at 120 to 125 ° C. for 6 hours. . After cooling the reaction solution to 55 ° C., 500 parts of methanol was added. The precipitated solid was collected by filtration and dried to obtain 54.9 parts of a compound represented by the following formula (15).

(Process 2)
In 140 parts of xylene, 54.9 parts of the compound represented by the formula (15) obtained in Example 4 (Step 1), 67.0 parts of ethyl benzoyl acetate, and 1.3 parts of potassium carbonate were sequentially added to raise the temperature. The reaction was conducted at 135 to 140 ° C. for 5 hours. Meanwhile, ethanol and water produced in the reaction were distilled out of the system while azeotroping with xylene to complete the reaction. The obtained reaction liquid was cooled, 250 parts of methanol was added at 60 ° C., and the mixture was stirred at 20 to 25 ° C. for 30 minutes. The precipitated solid was collected by filtration, washed with 350 parts of methanol, then with 100 parts of hot water at 50 ° C., and dried to obtain 53.4 parts of a compound of the following formula (16).

(Process 3)
26.1 parts of the compound represented by the formula (16) obtained in Example 4 (Step 2), 22.5 parts of 3-aminoacetanilide, copper acetate monohydrate 5 in 80 parts of N, N-dimethylformamide .6 parts and 3.5 parts of sodium carbonate were sequentially added and reacted at 120 to 130 ° C. for 5 hours. The obtained reaction liquid was cooled, 270 parts of methanol was added at 50 ° C., and the mixture was stirred at 20 to 25 ° C. for 30 minutes. The precipitated solid was collected by filtration, washed with 200 parts of methanol, then with 100 parts of hot water at 50 ° C., and dried to obtain 21.7 parts of a compound of the following formula (17).

(Process 4)
68.3 parts of 98% sulfuric acid was added to 83.5 parts of 32.7% fuming sulfuric acid to prepare 151.8 parts of 10% fuming sulfuric acid. 21.6 parts of the compound represented by the formula (17) obtained in Example 4 (Step 3) was added to the prepared liquid while maintaining a liquid temperature of 50 ° C. or lower under water cooling. The obtained liquid was heated to 90 to 95 ° C., reacted for 3 hours, cooled to room temperature, and added to 300 parts of ice water. To the obtained liquid, 98.2 parts of sodium chloride was added, and the precipitated solid was collected by filtration. The obtained solid was dissolved in 100 parts of ion-exchanged water, and anion exchange resin Diaion ^RTM SA10AOH 75 parts and cation exchange resin Diaion ^RTM SK1BH 26 parts (both manufactured by Mitsubishi Chemical Corporation) were added as appropriate to adjust the pH of the solution. It stirred at 20-25 degreeC for 2 hours, hold | maintaining at 6.0-8.0. The ion exchange resin was removed from the resulting liquid by filtration, 600 parts of isopropyl alcohol was added, and the precipitated solid was collected by filtration and dried to obtain 13.7 parts of a compound represented by the following formula (18). It was.

(Process 5)
To 30 parts of N, N-dimethylformamide is added 1.0 part of the compound represented by the formula (18) obtained in Example 4 (Step 4) and 0.1 part of ethylenediaminetetraacetic acid dianhydride, and 85 to 85 parts. The mixture was heated to 90 ° C. and reacted for 8 hours. The obtained reaction solution was added to 200 parts of 2-propanol, and the precipitated solid was collected by filtration to obtain 3.1 parts of a wet cake containing the compounds represented by the following formulas (19) and (20). Obtained.

(Step 6)
3.1 parts of a wet cake containing the compounds represented by formula (19) and formula (20) obtained in Example 4 (step 5) is added to 20 parts of water, and the pH of the solution is 8.0 with sodium carbonate. Adjusted. In this solution, 0.2 part of copper (II) acetate monohydrate was added, and the mixture was reacted at 25 to 30 ° C. for 2 hours while adjusting the pH to 6.5 to 7.5 using a 15% aqueous sodium carbonate solution. It was. 120 parts of isopropyl alcohol was added to the obtained reaction solution, and the precipitated solid was collected by filtration. The obtained solid was dissolved in 20 parts of water, 200 parts of 2-propanol was added, and the precipitated solid was collected by filtration and dried, whereby the compounds represented by the following formulas (21) and (22) were obtained. 0.8 parts of a red solid of the mixture were obtained. The HPLC area ratio of the compound represented by Formula (21) and Formula (22) in the obtained solid was 66/34.

λｍａｘ：５２６ｎｍ。

λmax: 526 nm.

[Example 5]
(Process 1)
To 30 parts of N, N-dimethylformamide, 2.0 parts of the compound represented by the formula (18) obtained in Example 4 (Step 4) and 0.1 part of ethylenediaminetetraacetic acid dianhydride are added, and 85-85 The mixture was heated to 90 ° C. and reacted for 16 hours. The obtained reaction solution was added to 230 parts of 2-propanol and the precipitated solid was collected by filtration to obtain 7.9 parts of a wet cake containing the compounds represented by the formulas (19) and (20). Obtained.

(Process 2)
7.9 parts of a wet cake containing the compound represented by the formula (19) and the formula (20) obtained in Example 5 (Step 1) was added to 40 parts of water, and the pH of the solution was 8.0 with sodium carbonate. Adjusted. To this solution, 0.3 parts of copper (II) acetate monohydrate was added, and the mixture was reacted at 25-30 ° C. for 2 hours while adjusting the pH to 6.5-7.5 using a 15% aqueous sodium carbonate solution. It was. To the obtained reaction solution, 170 parts of isopropyl alcohol was added, and the precipitated solid was collected by filtration. The obtained solid was dissolved in 40 parts of water, 280 parts of 2-propanol was added, and the precipitated solid was collected by filtration and dried, whereby the compounds represented by the above formulas (21) and (22) were obtained. 2.2 parts of a red solid of the mixture were obtained. The HPLC area ratio of the compounds represented by formula (21) and formula (22) in the obtained solid was 31/69.
λmax: 527 nm.

[Example 6]
(Process 1)
In 120 parts of N, N-dimethylformamide, 45.7 parts of the compound represented by the formula (14), 15.6 parts of 4-methylphenol, and 9.5 parts of potassium carbonate are added, and the mixture is heated at 120 to 125 ° C. Reacted for hours. After the reaction solution was cooled to 55 ° C., 250 parts of methanol was added. The precipitated solid was collected by filtration and dried to obtain 24.9 parts of a compound represented by the following formula (23).

(Process 2)
In 77 parts of xylene, 24.9 parts of the compound represented by the formula (23) obtained in Example 6 (Step 1), 29.3 parts of ethyl benzoyl acetate, and 0.5 part of potassium carbonate were sequentially added to raise the temperature. The reaction was conducted at 135 to 140 ° C. for 6 hours. Meanwhile, ethanol and water produced in the reaction were distilled out of the system while azeotroping with xylene to complete the reaction. The obtained reaction liquid was cooled, 180 parts of methanol was added at 60 ° C., and the mixture was stirred at 20 to 25 ° C. for 30 minutes. The precipitated solid was collected by filtration, washed with 200 parts of methanol, then with 70 parts of hot water at 50 ° C., and dried to obtain 29.5 parts of a compound of the following formula (24).

(Process 3)
29.5 parts of the compound represented by the formula (24) obtained in Example 6 (Step 2), 24.8 parts of 3-aminoacetanilide, 90 parts of N, N-dimethylformamide, copper acetate monohydrate 5 .8 parts and 3.6 parts of sodium carbonate were sequentially added, and the reaction was carried out at 120 to 130 ° C. for 6 hours. The obtained reaction liquid was cooled, 290 parts of methanol was added at 50 ° C., and the mixture was stirred at 20 to 25 ° C. for 30 minutes. The precipitated solid was collected by filtration, washed with 220 parts of methanol, then with 110 parts of hot water at 50 ° C., and dried to obtain 24.0 parts of a compound of the following formula (25).

(Process 4)
70.0 parts of 98% sulfuric acid was added to 86.0 parts of 32.7% fuming sulfuric acid to prepare 156.0 parts of 10% fuming sulfuric acid. Under cooling with water, 24.0 parts of the compound represented by the formula (25) obtained in Example 6 (Step 3) was added to the prepared liquid while maintaining a liquid temperature of 50 ° C. or lower. The obtained liquid was heated to 90 to 95 ° C., reacted for 3 hours, cooled to room temperature, and added to 300 parts of ice water. To the obtained liquid, 100.4 parts of sodium chloride was added, and the precipitated solid was collected by filtration. The obtained solid is dissolved in 110 parts of ion exchange water, and anion exchange resin Diaion ^RTM SA10AOH 75 parts and cation exchange resin Diaion ^RTM SK1BH26 parts (both manufactured by Mitsubishi Chemical Corporation) are added as appropriate to adjust the pH of the solution. It stirred at 20-25 degreeC for 2 hours, hold | maintaining at 6.0-8.0. The ion exchange resin was removed from the resulting liquid by filtration, 650 parts of isopropyl alcohol was added, and the precipitated solid was separated by filtration and dried to obtain 14.2 parts of the compound represented by the following formula (26). Obtained.

(Process 5)
To 130 parts of N-methylpyrrolidone, 5.0 parts of the compound represented by the formula (26) obtained in Example 6 (Step 4) and 0.7 parts of ethylenediaminetetraacetic acid dianhydride are added, and the mixture is heated to 80 to 85 ° C. The reaction was carried out for 10 hours by heating. The obtained reaction liquid was added to 200 parts of 2-propanol, and the precipitated solid was collected by filtration to obtain 2.9 parts of a wet cake containing the compounds represented by the following formulas (27) and (28). Obtained.

(Step 6)
3.1 parts of a wet cake containing the compounds represented by formulas (27) and (28) obtained in Example 6 (Step 5) was added to 30 parts of water, and the pH of the solution was adjusted to 8.0 with sodium carbonate. It was adjusted. To this solution, 0.4 part of copper (II) acetate monohydrate was added, and the mixture was reacted at 25-30 ° C. for 2 hours while adjusting the pH to 6.5-7.5 using a 15% aqueous sodium carbonate solution. It was. 120 parts of isopropyl alcohol was added to the obtained reaction solution, and the precipitated solid was collected by filtration. The obtained solid was dissolved in 20 parts of water, 300 parts of 2-propanol was added, and the precipitated solid was collected by filtration and dried, whereby the compounds represented by the following formulas (29) and (30) were obtained. 1.2 parts of a red solid of the mixture were obtained. The HPLC area ratio of the compound represented by Formula (29) and Formula (30) in the obtained solid was 25/75.

λｍａｘ：５２４ｎｍ。

λmax: 524 nm.

[Example 7] (A) Preparation of Ink An ink composition was prepared by mixing the components shown in Table 4 below, and a test ink was obtained by filtering through a 0.45 μm membrane filter. At this time, ion-exchanged water was used as the water, and the pH of the ink composition was adjusted using an aqueous sodium hydroxide solution to be 8 to 9, and water was added so that the total amount was 100.0 parts. An ink prepared by using the compound obtained in Example 1 as a coloring matter in the ink is referred to as Example 7. An ink was prepared in the same manner as in Example 7, except that the compound obtained in Example 2 to Example 6 was used instead of the compound obtained in Example 1. This is referred to as Example 8 to Example 12. In Table 3 below, “surfactant” manufactured by Nissin Chemical Co., Ltd., trade name Surfynol ^RTM 104PG50 was used.

[Comparative Example 1] Example 7 except that the compound represented by the formula (9) obtained in Example 1 (Step 1) was used in place of the compound of the present invention obtained in Examples 1 to 6. The ink for comparison was prepared in the same manner as in Example 12. This ink preparation is referred to as Comparative Example 1.

Comparative Example 2 Examples 7 to 12 except that the compound represented by the formula (18) obtained in Example 6 (Step 4) was used in place of the compounds of the present invention obtained in Examples 1 to 6. In the same manner as described above, a comparative ink was prepared. This ink preparation is referred to as Comparative Example 2.

(B) Inkjet recording Each of the inks obtained in each of the examples and comparative examples was used, and inkjet recording was performed on the following two types of glossy paper using a Canon inkjet printer and product name PIXUS ^RTM iP4500. It was. At the time of recording, an image pattern was prepared so that six gradation levels of 100%, 85%, 70%, 55%, 40%, and 25% density were obtained, and a halftone recorded matter was obtained. Using the obtained recorded matter as a test piece, the following test was conducted.

Glossy paper 1:
Product name Seiko Epson Co., Ltd. Photographic paper Krispia High gloss.
Glossy paper 2:
Brother Industries, Ltd., trade name photographic glossy paper BP71G.

(C) Various tests for colorimetry of recorded images and evaluations thereof were performed by measuring the color of a test piece using a colorimeter manufactured by X-rite Co., Ltd. and a trade name of SpectroEye ^RTM . Colorimetry was performed under the conditions of DIN, a viewing angle of 2 °, and a light source D65 as a density standard. The color measurement was performed on a 70% gradation portion in the image pattern of each test piece.

(D) Xenon light resistance test Each test piece was placed in a holder and a xenon weatherometer XL75 [manufactured by Suga Test Instruments Co., Ltd.] was used, and the temperature was 24 ° C., humidity 60% RH, 100 klux illuminance for 168 hours. Irradiated.
Using the colorimetry system after the test, the print density (Dm) before and after the test was measured to determine the dye residual ratio. The pigment remaining ratio is more excellent when the value is larger. The results are shown in Table 4 below. The dye residual ratio was calculated by the following formula.

Dye remaining rate = (print density after test / print density before test) × 100 (%)

(E) Ozone resistance test Each test piece was allowed to stand for 24 hours at an ozone concentration of 10 ppm, a bath temperature of 23 ° C., and a humidity of 50% RH using an ozone weather meter (model OMS-H manufactured by Suga Test Instruments Co., Ltd.). Using the colorimetry system after the test, the print density (Dm) before and after the test was measured to determine the dye residual ratio. The pigment remaining ratio is more excellent when the value is larger. The results are shown in Table 4 below. The dye residual ratio was calculated by the following formula. Dye remaining rate = (print density after test / print density before test) × 100 (%)

As is clear from the results in Table 4, the recorded images obtained using the inks of Examples 7 to 12 had a larger residual ratio than the comparative examples when any glossy paper was used, It was confirmed that it was excellent in light resistance and ozone resistance.
Therefore, the compound of the present invention and the ink composition containing the compound are suitable for various recordings, particularly for ink use for inkjet recording.

  The compound of the present invention and the ink composition of the present invention containing the compound are suitable for various recording applications, particularly for inkjet recording applications, because they provide a recorded image having excellent light resistance and ozone resistance.

Claims (12)

An ink composition containing at least one compound represented by the following formula (1) or a salt thereof as a pigment;

[In Formula (1),
R ¹ and R ² each independently represents a hydrogen atom or an alkyl group,
R ¹ and R ² may combine to form a cycloalkylene ring with the two carbon atoms that they each replace,
Group A represents a group represented by the following formula (2),
The group B represents a carboxy group or a group represented by the following formula (2). ],

[In Formula (2),
* Represents the binding site as group A;
n represents an integer of 0 or 1,
R ³ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, or a cyanoalkyl group,
R ⁴ represents a hydrogen atom, a halogen atom, a carboxy group, an alkyl group, an alkoxy group, or a sulfo-substituted phenyl group. ]. In equation (1),
R ¹ and R ² are each independently a hydrogen atom or a C1-C6 alkyl group,
R ¹ and R ² may combine to form a C5-C10 cycloalkylene ring with the two carbon atoms that each substitutes;
Group A is a group represented by Formula (2),
Group B is a carboxy group or a group represented by formula (2);
In equation (2),
* Is the binding site as group A;
n is an integer of 0 or 1,
R ³ is a hydrogen atom, a C1-C6 alkyl group, a hydroxy C1-C6 alkyl group, a cyclohexyl group, or a cyano C1-C6 alkyl group,
R ⁴ is a hydrogen atom, a halogen atom, a carboxy group, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a sulfo-substituted phenyl group.
The ink composition according to claim 1. In equation (2),
R ³ is a hydrogen atom or a C1-C6 alkyl group,
R ⁴ is a hydrogen atom, a C1-C6 alkyl group, or a sulfo-substituted phenyl group.
The ink composition according to claim 1 or 2. The ink composition according to any one of claims 1 to 3, further comprising a water-soluble organic solvent. The ink composition according to claim 1, which is used for inkjet recording. 6. An ink jet recording method for performing recording by ejecting the droplets of the ink composition according to any one of claims 1 to 5 in accordance with a recording signal to adhere to the recording material. 7. The ink jet recording method according to claim 6, wherein the recording material is an information transmission sheet. 8. The ink jet recording method according to claim 7, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance. A colored body colored with the ink composition according to any one of claims 1 to 5. A colored body colored by the ink jet recording method according to claim 6. An inkjet printer loaded with a container containing the ink composition according to any one of claims 1 to 5. A compound represented by the following formula (1) or a salt thereof,

[In Formula (1),
R ¹ and R ² each independently represents a hydrogen atom or an alkyl group,
R ¹ and R ² may combine to form a cycloalkylene ring with the two carbon atoms that they each replace,
The group A is a group represented by the following formula (2), and the group B represents a carboxy group or a group represented by the following formula (2). ],

[In Formula (2),
* Represents the binding site as group A;
n represents an integer of 0 or 1,
R ³ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, or a cyanoalkyl group,
R ⁴ represents a hydrogen atom, a halogen atom, a carboxy group, an alkyl group, an alkoxy group, or a sulfo-substituted phenyl group. ].