JP4446339B2 - Azo compound, ink composition - Google Patents

Description

  The present invention relates to a novel azo compound or a salt thereof, an ink composition containing these, and a colored product thereby.

  A recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is what you do. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material do not contact each other and is quiet with little sound generation, and is easy to downsize and speed up. Expected. Conventionally, water-based inks in which water-soluble dyes are dissolved in an aqueous medium have been used as inks such as fountain pens, felt-tip pens, and ink-jet recording inks. In order to prevent clogging of ink, a water-soluble organic solvent is generally added. Therefore, in these conventional inks, it is possible to provide a recording image having a sufficient density, no clogging of the pen tip and nozzles, good drying on the recording material, less bleeding, The storage stability is required to be excellent, and particularly, the solubility in water is high, and the solubility in a water-soluble organic solvent added to the ink is required. If the solubility in water or a water-soluble organic solvent is low, a bronzing phenomenon (a phenomenon in which the surface of a glossy paper is glazed due to the association of dyes or the like) occurs, and the print quality is significantly reduced. Further, the formed image is required to have image fastness such as water resistance, light resistance, ozone gas resistance and moisture resistance.

Ozone gas resistance, also called ozone resistance or gas resistance, is the resistance to the phenomenon that ozone gas with an oxidizing action that exists in the air acts on the dye in the recording paper, causing the printed image to fade and fade. That's it. In addition to ozone gas, examples of the oxidizing gas having this kind of action include NOx and SOx. Among these oxidizing gases, ozone gas further promotes the discoloration and discoloration phenomenon of ink jet recorded images. It is considered a substance. In particular, the ink receiving layer provided on the surface of photographic image quality inkjet paper uses a porous material such as a white inorganic pigment to speed up ink drying and reduce bleeding at high image quality. In many cases, discoloration due to ozone gas is noticeable on such recording paper.
This is because ozone contained in the air comes into contact with porous white inorganic silica or alumina contained in the recording paper to generate radicals with a strong oxidizing action, which act on the dye, causing discoloration and discoloration. It seems to be. Since the discoloration phenomenon due to the oxidizing gas is characteristic of ink jet images, improvement of ozone gas resistance is one of the most important issues in ink jet recording.

  In the future, in order to expand the field of use of printing methods using ink, the ink composition used for inkjet recording and the colored bodies colored thereby will be further improved in water resistance, light resistance, moisture resistance and ozone gas resistance. There is a strong demand for improvement.

  Applications are expanding with the widespread use of inkjet recording methods. Until now, there have been three colors of yellow, magenta and cyan, or four colors including black, but the use of multi-color inks such as red, green, blue and orange is being studied. In other words, the challenge of faithfully reproducing all colors in nature is continuing. In order to meet this demand, various dyes and inks that can reproduce all hues, colors, and densities are required. There is also a need for dyes for toning yellow to red components for constituting high quality black to gray achromatic colors. As a dye for toning a yellow to orange dye to a black dye, for example, there is a dye of the following formula (4) that can be produced by the method described in Patent Document 1, but this dye is a product that sufficiently satisfies market demands. It has not been provided.

Japanese Patent Publication No.33-7643

  The present invention has high solubility in a medium containing water as a main component, is stable even when a high-concentration dye aqueous solution and ink are stored for a long period of time, has high printed image density, and does not cause bronzing, printing An object of the present invention is to provide a yellow to red ink coloring matter and an ink composition thereof that give a recorded image excellent in fastness of the formed image, in particular, ozone gas resistance, and can be easily synthesized.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific azo dye can solve the above problems, and have reached the present invention.

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

(In Formula (1), R ¹ is a hydrogen atom; a hydroxyl group; a carboxyl group; a hydroxyl group or a (C1-C4) alkyl group optionally substituted by an alkoxy group; a hydroxyl group or (C1- C4) (C1-C4) alkoxy group optionally substituted by an alkoxy group; (C1-C4) alkylamino group optionally substituted by a hydroxyl group or (C1-C4) alkoxy group; carboxy- (C1- C5) alkylamino group; bis- [carboxy- (C1-C5) alkyl] amino group; hydroxyl group or (C1-C4) alkanoylamino group optionally substituted by an alkoxy group; carboxyl group; A phenylamino group optionally substituted with a sulfo group or an amino group; a sulfo group (—SO ₃ H); A halogen atom or a ureido group, A is an aliphatic or aromatic amine residue or hydroxyl group which may have a substituent, and B is an aliphatic or aromatic amine residue or mono which may have a substituent. Or each represents a residue of a disazo compound.)
(2) The azo compound or salt thereof according to (1), wherein A is an aliphatic amine residue or hydroxyl group having a carboxyl group or a sulfonic acid group, and B is a residue of a mono- or disazo compound,
(3) An azo compound represented by the following formula (2) or a salt thereof,

(In formula (2), R ¹ represents the same meaning as in formula (1), and A ′ represents an aliphatic amine residue having a carboxyl group or a sulfonic acid group or a hydroxyl group.)
(4) The salt of the azo compound according to any one of (1) to (3), wherein the salt is a lithium salt, a sodium salt, a potassium salt, an ammonium salt, or an ammonium salt represented by the general formula (3),

(In formula (3), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a hydroxyalkoxyalkyl group.)
(5) An ink composition comprising the compound or salt thereof according to any one of (1) to (4),
(6) An ink jet recording method using the ink composition according to (5),
(7) The inkjet recording method according to (6), wherein the recording material in the inkjet recording method is an information transmission sheet;
(8) The ink jet recording method according to (7), wherein the information transmission sheet contains a porous white inorganic substance,
(9) An ink jet printer loaded with the ink composition according to (5),
(10) A colored body colored with the azo compound or a salt thereof according to any one of (1) to (4),
About

  Since the azo compound of the present invention is excellent in water solubility, it has good filterability with a membrane filter in the production process of the ink composition, and is excellent in stability during storage and ejection stability of the recording liquid. Further, the ink composition of the present invention containing this azo compound has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage. The ink composition containing the azo compound of the present invention is used for ink jet recording and writing instruments, and has a high print density of recorded images when recorded on plain paper and ink jet dedicated paper, and gloss used for photographic recording. Even paper does not cause bronzing. Furthermore, when used together with various fastness properties, particularly magenta, cyan, and yellow dyes that are excellent in ozone gas resistance, full-color ink jet recording with a wide color range excellent in various fastness properties is possible. As described above, the azo compound of the present invention is useful as a dye for obtaining a wide hue of yellow to red, or as a dye (toning dye) for adjusting a slight difference in color tone. Prepared into a composition for use.

  Hereinafter, the present invention will be described in detail.

In the compound of formula (1) of the present invention,
R ₁ is a hydrogen atom; a hydroxyl group; a carboxyl group; a hydroxyl group or a (C1-C4) alkyl group optionally substituted by a (C1-C4) alkoxy group; a hydroxyl group or a (C1-C4) alkoxy group. An optionally substituted (C1-C4) alkoxy group; a hydroxyl group or a (C1-C4) alkylamino group optionally substituted by a (C1-C4) alkoxy group; a carboxy- (C1-C5) alkylamino group; -[Carboxy- (C1-C5) alkyl] amino group; hydroxyl group or (C1-C4) alkanoylamino group optionally substituted by (C1-C4) alkoxy group; phenyl group is carboxyl group, sulfo group or amino group A phenylamino group optionally substituted with a group; a sulfo group; a halogen atom or The ureido group
A is an aliphatic or aromatic amine residue or hydroxyl group which may have a substituent, and B is an aliphatic or aromatic amine residue which may have a substituent or the residue of a mono- or disazo compound. Group
Each is shown.

In the above, specific examples of the (C1-C4) alkyl group optionally substituted by a hydroxyl group or a (C1-C4) alkoxy group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -Butyl, tert-butyl, methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, sec-butoxyethyl, tert-butoxyethyl, 2-hydroxyethyl and the like can be mentioned.
Examples of the (C1-C4) alkoxy group optionally substituted by a hydroxyl group or a (C1-C4) alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, Examples include isopropoxybutoxy, n-propoxybutoxy, 2-hydroxyethoxyethoxy and the like.
Furthermore, examples of the (C1-C4) alkylamino group optionally substituted by a hydroxyl group or a (C1-C4) alkoxy group include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino. , Isobutylamino, N, N-dimethylamino, N, N-diethylamino, N, N-di (n-propyl) amino, N, N-di (isopropyl) amino, hydroxyethylamino, 2-hydroxypropylamino, 3 -Hydroxypropylamino, bis (hydroxyethyl) amino, methoxyethylamino, ethoxyethylamino, bis (methoxyethyl) amino, bis (2-ethoxyethyl) amino and the like.
Furthermore, examples of the carboxy- (C1-C5) alkylamino group include carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxy-n-butylamino, carboxy-n-pentylamino and the like.
Furthermore, examples of the bis- [carboxy- (C1-C5) alkyl] amino group include bis- (carboxymethyl) amino, bis- (carboxyethyl) amino, bis- (carboxypropyl) amino and the like.
Furthermore, examples of the (C1-C4) alkanoylamino group optionally substituted by a hydroxyl group or a (C1-C4) alkoxy group include acetylamino, n-propionylamino, isopropionylamino, hydroxyacetylamino, 2-hydroxy -N-propionylamino, 3-hydroxy-n-propionylamino, 2-methoxy-n-propionylamino, 3-methoxy-n-propionylamino, 2-hydroxy-n-butyrylamino, 3-hydroxy-n-butyrylamino, 2 -Methoxy-n-butyrylamino, 3-methoxy-n-butyrylamino and the like.
Furthermore, examples of the phenylamino group in which the phenyl group may be substituted with a carboxyl group, a sulfo group or an amino group include phenylamino, sulfophenylamino, carboxyphenylamino, biscarboxyphenylamino, aminophenylamino, diaminophenyl Examples include amino and diaminosulfophenylamino.
Furthermore, specific examples of the aliphatic amine residue which may have a substituent include sulfomethylamino, sulfoethylamino, 2-sulfopropylamino, 3-sulfopropylamino, sulfo-n-butylamino, sulfo -N-pentylamino, bis-sulfomethylamino, bis- (sulfoethyl) amino, bis- (sulfopropyl) amino, n-propionylamino, isopropionylamino, hydroxyacetylamino, 2-hydroxy-n-propionylamino, 3 -Hydroxy-n-propionylamino, 2-methoxy-n-propionylamino, 3-methoxy-n-propionylamino, 2-hydroxy-n-butyrylamino, 3-hydroxy-n-butyrylamino, 2-methoxy-n-butyrylamino, 3-methoxy-n-butyrylamino Carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxy-n-butylamino, carboxy-n-pentylamino, bis- (carboxymethyl) amino, bis- (carboxyethyl) amino, bis- (carboxypropyl) amino, etc. Is mentioned.
Furthermore, specific examples of the aromatic amino residue which may have a substituent include phenylamino, 2-, 3-, or 4-sulfophenylamino, 2-, 3-, or 4-carboxyphenylamino. 3,5-biscarboxyphenylamino, 3-, or 4-aminophenylamino, 3,5-diaminophenylamino, 2-, 3-, or 4-hydroxyphenylamino, 2-carboxy-4-hydroxyphenylamino , 2-carboxy-4-sulfophenylamino and the like.
Furthermore, the mono- or disazo compound is preferably selected from residues of monoazo compounds or disazo compounds having a hydrophilic group such as a carboxyl group and a sulfo group and having an amino group.

Among these, as preferred for R ₁ , a methyl group, an ethyl group, and an n-propyl group, and for A and B, an aliphatic amine residue having a carboxyl group or a sulfo group, a hydroxyl group, or those described later The group (—NH) of the disazo compound represented by the formula (7) is preferable, and more preferable groups include groups shown in Table 1 and Table 2 ((1) to (3)) described later.

The azo compound of the present invention represented by the general formulas (1) and (2) can be synthesized, for example, by the following method. Here, the azo compound represented by the general formula (2) will be described as an example, but the azo compound represented by the general formula (1) can also be synthesized by the same method as described herein. The structural formula of each compound is expressed in the form of a free acid.
That is, Formula (5)

Is diazotized by a conventional method to obtain a compound of formula (6)

Formula (7) produced by a coupling reaction with the compound represented by

To the compound represented by the formula (8)

The compound represented by the formula (7) is subjected to a condensation reaction, and the formula (9)

To obtain a compound represented by: The compound represented by the formula (2) is obtained by adding and condensing the aliphatic amine (corresponding to A) having the above carboxyl group or sulfo group under alkaline conditions.

  Examples of the residue of any aliphatic or aromatic amino compound are not particularly limited as described above, but preferred specific examples include the following groups.

  Preferable examples of the residue of the mono to disazo compound include the following groups.

  The diazotization of the compound of formula (5) is carried out in a manner known per se, for example nitrites, such as sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 40 ° C., preferably 5 to 25 ° C. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of formula (5) with the compound of formula (6) is also carried out under conditions known per se. It is advantageous to carry out in an aqueous or aqueous organic medium, for example at a temperature of -5 to 30 [deg.] C, preferably 5 to 20 [deg.] C and an acidic to neutral pH value. Preferably, it is carried out at a weakly acidic to neutral pH value, for example, pH 2-6. The pH value is adjusted by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia and organic amines. . The compounds of formulas (5) and (6) are used in approximately stoichiometric amounts.

  The reaction of the compound of formula (7) with cyanuric chloride is also carried out under conditions known per se. It is carried out in an aqueous or organic medium, for example at a temperature of 0 to 40 ° C., preferably 0 to 30 ° C. and a pH of 1 to 7, preferably a pH of 3 to 7. The compound of formula (7) and cyanuric chloride are used in approximately stoichiometric amounts.

  The reaction between the compound of formula (7) and the compound of formula (8) is also carried out under conditions known per se. It is carried out in an aqueous or organic medium, for example at a temperature of 10-60 ° C., preferably 20-45 ° C. and a pH of 3-10, preferably pH 6-8. The compounds of formulas (7) and (8) are used in approximately stoichiometric amounts.

  The reaction of the compound of the formula (9) with an aliphatic amine having any carboxyl group or sulfo group is also carried out under conditions known per se. It is carried out in an aqueous or organic medium, for example at a temperature of 30-100 ° C., preferably 50-95 ° C. and a pH of 5-13, preferably pH 6-11. The compound of formula (9) and the optional aliphatic amine are used at 1: 1.5 to 3.0.

The azo compound represented by the general formula (1) or (2) according to the present invention or a salt thereof (hereinafter, unless otherwise specified, the compounds of the general formulas (1) and (2) or salts thereof are collectively referred to as “the compound of the present invention”). Can be isolated in the form of the free acid by the addition of mineral acid after the coupling reaction, and the inorganic salts can be removed therefrom by washing with water or acidified water. Next, the acid type dye having a low salt content thus obtained can be neutralized with a desired inorganic or organic base in an aqueous medium to obtain a solution of the corresponding salt. Examples of inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate. Examples of organic bases include organic amine salts and alkanolamine salts.
Preferred salts of amines include salts represented by the above formula (3). In the salt represented by the formula (3), Z ¹ , Z ² , Z ³ and Z ⁴ independently represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a hydroxyalkoxyalkyl group. Here, specific examples of Z ¹ , Z ² , Z ³ and Z ⁴ include a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hydroxymethyl group , Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxybutyl group, hydroxyethoxymethyl group, 2-hydroxyethoxyethyl group, 3-hydroxy Examples include ethoxypropyl group, 2-hydroxyethoxypropyl group, 4-hydroxyethoxybutyl group, 3-hydroxyethoxybutyl group, 2-hydroxyethoxybutyl group and the like.

Next, the ink composition of the present invention and the inkjet ink will be described.
The aqueous composition containing the compound of the present invention can dye a material composed of cellulose. In addition, other materials having a carbonamide bond can be dyed, and can be widely used for dyeing leather, fabrics and paper. On the other hand, a preferred use of the compound of the present invention is an ink composition that is dissolved in a liquid medium.

  The reaction liquid containing the compound of the present invention can be used directly in the production of a recording ink composition. However, it is first isolated by drying, eg spray drying, or salted out with inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate or acidified with mineral acids such as hydrochloric acid, sulfuric acid, nitric acid. Alternatively, the azo compound of the present invention can be taken out by acid salting out by combining salting out and aciding out, and then processed into an ink composition.

  The ink composition of the present invention is a composition mainly containing water containing 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass of the compound of the present invention. is there. The ink composition of the present invention may further contain, for example, 0 to 30% by mass of a water-soluble organic solvent and 0 to 5% by mass of an ink preparation agent, for example. The pH of the ink composition is preferably pH 6 to 10 and more preferably pH 7 to 10 for the purpose of improving storage stability. Further, the surface tension of the ink composition is preferably 25 to 70 mN / m, and more preferably 25 to 60 mN / m. Furthermore, the viscosity of the ink composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less.

  The aqueous ink composition of the present invention is obtained by dissolving the compound of the present invention in water or a water-soluble organic solvent (an organic solvent miscible with water), and adding an ink preparation agent as necessary. The pH of the aqueous ink composition of the present invention is preferably about 5 to 11. When this water-based ink composition is used as an ink for an ink jet printer, it is preferable to use a compound containing a small amount of an inorganic substance such as a metal cation chloride or sulfate as the compound of the present invention. Is, for example, about 1% by mass or less (to the chromogen). In order to produce the compound of the present invention with a small amount of inorganic substances, for example, a usual method using a reverse osmosis membrane or a dried product or wet cake of the compound of the present invention is stirred in a mixed solvent of alcohol such as methanol and water, filtered and dried. What is necessary is just to desalinate by the method of carrying out.

  Examples of water-soluble organic solvents that can be used in the preparation of the ink composition include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butanol, and N, N-dimethylformamide. Or carboxylic acid amides such as N, N-dimethylacetamide, lactams such as 2-pyrrolidone and N-methylpyrrolidin-2-one, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido Cyclic ureas such as 2-one, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or cyclic ethers such as keto alcohol, tetrahydrofuran, dioxane, ethylene glycol, 1,2-propylene Glycol, 1,3 Propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, dithio Monomers, oligomers or polyalkylene glycols or thioglycols having (C2-C6) alkylene units such as diglycol, polyols (triols) such as glycerin, hexane-1,2,6-triol, ethylene glycol monomethyl ether or ethylene glycol mono Ethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether or triethylene glycol monomethyl Polyhydric alcohol (C1 -C4) alkyl ethers such as ether or triethylene glycol monoethyl ether, gamma-butyrolactone or dimethyl sulfoxide and the like. These organic solvents may be used alone or in combination of two or more.

  In the preparation of the ink composition, if necessary, examples of the ink preparation agent used include, for example, antifungal agents, antiseptics, antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble ultraviolet absorptions. Agents, water-soluble polymer compounds, dye solubilizers, antioxidants, surfactants and the like. Specific examples and usage amounts of each drug that can be used will be described below.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the coloring composition in an amount of 0.02 to 1.00% by mass.

Examples of preservatives include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, and 8-oxyquinoline. , Benzothiazole, isothiazoline, dithiol, pyridine oxyd, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts. Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine oxido compound include sodium 2-pyridinethiol-1-oxide, and examples of the inorganic salt compound include anhydrous sodium acetate. Examples of the isothiazoline-based compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Can be mentioned.
Other antiseptic / antifungal agents include sodium sorbate, sodium benzoate and the like.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink within a range of, for example, 5 to 11 without adversely affecting the prepared ink. Examples include alkanolamines such as diethanolamine, triethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide (ammonia), or lithium carbonate. And alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate, and inorganic bases such as potassium acetate, sodium silicate and disodium phosphate.

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 compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.
Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.
Examples of the dye solubilizer include ε-caprolactam, ethylene carbonate, urea and the like.

  As the antioxidant, for example, various organic and metal complex antifading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic rings.

  Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants. Examples of the anionic surfactant include alkyl sulfonic acid, alkyl carboxylate, α-olefin sulfonate, polyoxyethylene alkyl ether acetate, N-acyl amino acid and its salt, N-acyl methyl taurate, alkyl sulfate polyoxy Alkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylallylsulfone hydrochloride, diethylsulfone Acid salts, dioctyl sulfosuccinate diethyl hexylsilsulfosuccinate and the like. Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives. Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyallylalkyl. Ethers such as alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate Esters, polyoxyethylene stearate, 2,4,7,9-tetramethyl-5-decyne-4,7-di Acetylene glycols such as 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol (for example, Surfhinol 104, 105 manufactured by Nisshin Chemical Co., Ltd.) 82, 465, Olfin STG, etc.). These ink preparation agents are used alone or in combination.

  The aqueous ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order. The obtained ink composition may be filtered with a membrane filter or the like, if desired, in order to remove impurities. Further, in order to prepare an ink composition having a hue of each color, it may be used by mixing with other pigments having various hues. That is, in addition to the compound of the present invention, it can be used by mixing with compounds (pigments) of other colors such as yellow, magenta, cyan, black and other colors.

  The ink composition of the present invention can be used in various fields, but is suitable for a water-based ink for writing, a water-based printing ink, an information recording ink, and the like, and is used as an ink-jet ink containing the ink composition. It is particularly preferred. Therefore, the inkjet ink of the present invention is characterized by containing the ink composition of the present invention, and the inkjet ink of the present invention is suitably used in the inkjet recording method of the present invention described later.

Next, the ink jet recording method of the present invention will be described.
The ink jet recording method of the present invention is characterized in that recording is performed using an ink jet ink containing the ink composition. In the ink jet recording method of the present invention, recording is performed on an image receiving material using an ink jet ink containing the ink composition, but there are no particular restrictions on the ink nozzles used at that time, depending on the purpose. Known methods, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, and an electrical signal An acoustic ink jet system that converts ink into an acoustic beam and irradiates the ink by using radiation pressure to eject the ink, thermal ink jet that forms bubbles by heating the ink and uses the generated pressure (Bubble Jet (registered trademark)) A method or the like can be used. The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent. A method using ink is included.

The colored product of the present invention is colored with the compound of the present invention or an ink composition containing the compound, and more preferably is colored with an ink jet printer using the ink composition of the present invention. Examples of materials that can be colored include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and base materials for color filters. The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer. In the ink receiving layer, porous white inorganic fine particles that can absorb the pigment in the ink such as porous silica, alumina sol, and special ceramics by impregnating or coating the base material with a cationic polymer, for example. It is provided by coating the surface of the substrate together with a hydrophilic polymer such as polyvinyl alcohol or polyvinyl pyrrolidone. Specific examples of porous white inorganic materials used for coating 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 and the like.
Those provided with such an ink receiving layer are usually called ink jet dedicated paper (film), glossy paper (film), etc., for example, Pictorico (manufactured by Asahi Glass Co., Ltd.), professional photo paper PR-101, super photo paper, Matte photo paper (all manufactured by Canon Inc.), PM photo paper (glossy), PM matte paper (all manufactured by Seiko Epson Corp.), Premium Plus Photo Paper, Premium Glossy Film, Photo Paper (all by Hewlett-Packard Japan) -It is marketed as Photo-like QP (made by Konica Corporation) etc. by Packard Co., Ltd. Of course, plain paper can also be used.

  The compound of the present invention is excellent in water solubility, and the ink composition of the present invention containing the compound of the present invention has good storage stability without crystal precipitation, physical property change, color change, etc. after long-term storage. The recording ink liquid containing the azo compound of the present invention is used for ink jet recording and writing instruments, and has a high print density when recorded on plain paper and ink jet exclusive paper, and further has ozone gas resistance, light resistance and moisture resistance. Excellent in properties.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following examples. In the text, “parts” and “%” are based on weight unless otherwise specified.

Example 1
After dissolving 35.7 parts of the compound of the formula (10) in 400 parts of water while adjusting the pH to 5.5 to 8.0 with sodium hydroxide, the temperature is adjusted to 15 to 25 ° C., and 41.7 parts of 35% hydrochloric acid, 40 Diazotization was performed by adding 18.9 parts of an aqueous sodium nitrite solution.

  To this diazo solution was added 24.5 parts of the compound of formula (11). During the addition, the pH value of the solution was maintained at 2.0 to 3.0 with liquid caustic soda. After completion of the addition, the mixture was further stirred at 15 to 30 ° C. for 3 hours at pH 5.0 to 7.0 to complete the coupling reaction, thereby obtaining a reaction solution containing the compound of the formula (12). Thereafter, sodium chloride was added for salting out, followed by filtration and then drying to obtain 55.2 parts of a monoazo compound of the formula (12).

  Next, 27.0 parts of the compound of the formula (12) obtained above are added to 1000 parts of water, adjusted to pH = 6.0-7.0 with liquid caustic soda, and cyanuric chloride 8 at 10-20 ° C. .9 parts were added. After the addition, the pH was maintained at 6.0 to 7.5 with sodium carbonate, and the mixture was stirred for 2 hours to obtain a solution containing the compound of the formula (13).

  The solution was heated to 30-40 ° C. and 28.0 parts of the compound of formula (12) were added. After the addition, the pH was maintained at 7.0 to 8.5 with sodium carbonate and stirred for 3 hours to obtain a solution containing the compound of formula (14).

  The solution was heated to 80-95 ° C. and 8.3 parts of taurine was added. After the addition, the pH was maintained at 9.0 to 10.0 with sodium carbonate, stirred for 6 hours, salted out with sodium chloride, and filtered. The total amount of the cake obtained was dissolved in 300 parts of water, crystallized with 600 parts of 2-propanol, desalted and then dried to obtain 38.8 parts of the compound of formula (15). The maximum absorption wavelength of this compound in water was 437 nm.

Example 2
38.5 parts of the compound of formula (16) were obtained in the same manner as described above except that 8.3 parts of taurine of Example 1 was changed to 17.9 parts of iminodiacetic acid. The maximum absorption wavelength of this compound in water was 436 nm.

Example 3
In the step of synthesizing the compound of formula (14) of Example 1, in the same manner as in Example 1, except that 19.4 parts of the compound of formula (17) are used instead of the compound of formula (12) 33.0 parts of compound (18) was obtained. The maximum absorption wavelength of this compound in water was 399 nm.

Example 4
In the step of synthesizing the compound of formula (14) of Example 1, the compound of formula (19) was used in the same manner as in Example 1, except that 25.9 parts of the compound of formula (19) were used instead of the compound of formula (12). 35.4 parts of compound (20) were obtained. The maximum absorption wavelength of this compound in water was 418 nm.

Example 5
In the step of synthesizing the compound of the formula (14) of Example 1, the compound of the formula (22) was prepared in the same manner as in Example 1, except that 14.2 parts of the compound of the formula (21) was used instead of the compound of the formula (12). ) 29.8 parts of The maximum absorption wavelength of this compound in water was 398 nm.

Example 6
In the step of synthesizing the compound of the formula (14) of Example 1, the method of Example 1 was repeated except that 20.5 parts of the compound of the formula (23) was used instead of the compound of the formula (12). 28.5 parts of compound 24) were obtained. The maximum absorption wavelength of this compound in water was 420 nm.

Example 7
In the synthesis step of the compound of the formula (14) of Example 1, 20.9 parts of the compound of the formula (25) instead of the compound of the formula (12), and 8.3 parts of taurine in the synthesis step of the compound of the formula (15). 32.5 parts of the compound of formula (26) were obtained in the same manner as in Example 1 except that 4.12 parts of monoethanolamine was used instead of. The maximum absorption wavelength of this compound in water was 488 nm.

Example 8
In the synthesis step of the compound of formula (14) of Example 1, 25.3 parts of the compound of formula (27) are used instead of the compound of formula (12), and in the synthesis step of the compound of formula (15) The mixture was heated to 80 to 95 ° C., maintained at pH = 10.0 to 11.0 with liquid caustic soda, stirred for 6 hours, salted out with sodium chloride, and filtered. The total amount of the cake obtained was dissolved in 300 parts of water and crystallized with 700 parts of 2-propanol for desalting and then dried to obtain 30.9 parts of the compound of formula (28). The maximum absorption wavelength of this compound in water was 517 nm.

Examples 9-16
(A) Preparation of ink An ink composition was prepared by mixing the following components, and filtered through a 0.45 μm membrane filter to obtain an aqueous ink composition of the invention for inkjet. The water used was ion exchange water. Water and ammonium hydroxide were added so that the pH of the ink composition was pH = 8-9.

Table 3
5.0 parts of each compound obtained in the above Example (uses desalted)
Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surfinol 105 manufactured by Nisshin Chemical Co., Ltd.) )
Water + aqueous ammonium hydroxide 75.9 parts Total 100.0 parts

  In Table 3, the compounds obtained in the above examples are compounds of the formula (15) in Example 9, compounds of the formula (16) in Example 10, and compounds of the formula (18) in Example 11. Example 12 is a compound of formula (20), Example 13 is a compound of formula (22), Example 14 is a compound of formula (24), Example 15 is a compound of formula (26), Example 16 shows the compound of the compound of formula (28), respectively. The pH during ink preparation was adjusted to 8-9 with ammonium hydroxide. This aqueous ink composition did not cause precipitation separation during storage, and did not change its physical properties even after long-term storage.

(B) Inkjet printing Using each of the ink compositions obtained above, by using an inkjet printer (trade name Canon BJ-S630), plain paper (Canon LBP PAPER LS-500), exclusive glossy paper PR (Canon) Inkjet recording was performed on three types of paper: Professional Photo Paper PR-101) and exclusive glossy paper PM (EPSON PM Photo Paper (Glossy) KA420PSK).
At the time of printing, each ink was refilled into a black ink cartridge, and an image pattern was created so that gradations with several levels of reflection density were obtained, thereby obtaining a halftone printed matter. Since the gray scale mode is used at the time of printing, the yellow, cyan, and magenta recording liquids other than the recording liquid are not printed in this light color portion. Among the test methods described below, the bronzing property was evaluated by observing the surface of the printed part with the highest density. When measuring the light resistance test and the ozone gas resistance test, which are items to be evaluated using a colorimeter, the measurement is performed using the gradation portion where the reflection density D value of the printed material before the test is closest to 1.0. went.

(C) Evaluation of recorded image
The recorded image by the aqueous ink composition of the present invention was evaluated for three points: bronzing, density residual ratio after light resistance test, and density residual ratio after ozone gas resistance test. The bronzing and ozone gas resistance tests were conducted only on the special glossy papers PR and PM. The results are shown in Table 4. The test method is shown below.
(A) The bronzing-specific glossy paper was evaluated according to the following criteria by observing the surface of the highest density portion.
○ The printed part shows the same glossiness as the non-printed part △ The printed part has a considerably deteriorated glossy state compared to the non-printed part × The printed part has a metallic glare and has no gloss (B) Light resistance test A xenon weatherometer Ci4000 (manufactured by ATLAS) was used to irradiate a print sample at an illuminance of 0.36 W / square meter for 50 hours. After the test was completed, the residual ratio of the density after the test was measured using the above colorimetric system. The determination was made based on the following.
○ Residual rate: 95% or more Δ Residual rate is less than 95% to 90% or more × Residual rate: less than 90% (c) Ozone gas resistance test Ozone concentration is 40 ppm using ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.) The print sample was left for 6 hours at a humidity of 60% RH and a temperature of 24 ° C. After the test, the density residual rate after the test was measured using the above colorimetric system. The determination was made based on the following.
○ Residual rate after 6 hours of test time is 85% or more △ Residual rate after 6 hours of test time is less than 85% to 70% or more x Residual rate after 6 hours of four houses is less than 70%

Comparative Example 1
As a comparative object, an ink composition having the same ink composition as in Examples 9 to 16 was prepared using Formula (4), which can be produced by the method described in Patent Document 1, as a water-soluble inkjet dye. Table 4 shows the results of printing density evaluation, light resistance evaluation, and ozone gas resistance evaluation of the recorded images obtained.

Table 4
Bronzing Light resistance Ozone gas resistance Example 9 (Formula (15))
Plain paper ― ○ −
Exclusive glossy paper PR ○ ○ △
Exclusive glossy paper PM ○ ○ ○
Example 10 (Formula (16))
Plain paper ― ○ −
Exclusive glossy paper PR ○ ○ △
Exclusive glossy paper PM ○ ○ ○
Example 11 (Formula (18))
Plain paper ― ○ −
Special glossy paper PR ○ △ ○
Exclusive glossy paper PM ○ ○ ○
Example 12 (Formula (20))
Plain paper ― ○ −
Exclusive glossy paper PR ○ ○ △
Exclusive glossy paper PM ○ ○ ○
Example 13 (Formula (22))
Plain paper ― ○ −
Special glossy paper PR ○ △ △
Exclusive glossy paper PM ○ ○ ○
Example 14 (Formula (24))
Plain paper ― ○ −
Special glossy paper PR ○ △ △
Exclusive glossy paper PM ○ ○ ○
Example 15 (Formula (26))
Plain paper ― ○ −
Exclusive glossy paper PR ○ △ ×
Exclusive glossy paper PM ○ ○ △
Example 16 (Formula (28))
Plain paper-△-
Exclusive glossy paper PR ○ △ ×
Special glossy paper PM ○ △ △
Comparative Example 1 (Formula (4))
Plain paper-No-
Exclusive glossy paper PR × × △
Exclusive glossy paper PM × △ ○

  Table 4 shows the following. Since Comparative Example 1 has low solubility, bronzing occurs on glossy paper. The product of the present invention has high solubility and no bronzing has occurred. The ink composition containing the compound of the present invention is excellent in light resistance and ozone gas resistance as compared with known similar dyes (comparative examples). .

  The ink composition containing the compound of the present invention is used as an ink liquid for ink jet recording and writing instruments.

Claims (9)

An azo compound represented by the following formula (1) or a salt thereof ,

(In formula (1), R ₁ represents a (C1-C4) alkyl group, A represents any one amine residue or hydroxyl group selected from the following formulas (A-1) to (A-7) , B represents any one residue selected from the following formulas (B-1) to (B-16 ) .

An azo compound represented by the following formula (2) or a salt thereof ,

(In the formula (2), R ₁ is a (C1-C4) alkyl group , and A ′ is any one amine residue or hydroxyl group selected from the following formulas (A-1) to (A-7): indicating each.).

The salt of the azo compound according to any one of claims 1 and 2 , wherein the salt is a lithium salt, a sodium salt, a potassium salt, an ammonium salt, or an ammonium salt represented by the general formula (3) .

(In the formula (3) represents ^{Z 1, Z 2, Z 3} , Z 4 are each independently a hydrogen atom, an alkyl group, hydroxyalkyl group or hydroxyalkoxyalkyl group.). An ink composition comprising the compound or a salt thereof according to any one of claims 1 to 3 . An ink jet recording method using the ink composition according to claim 4 . 6. The ink jet recording method according to claim 5 , wherein the recording material in the ink jet recording method is an information transmission sheet . The inkjet recording method according to claim 6 , wherein the information transmission sheet contains a porous white inorganic substance . An ink jet printer loaded with the ink composition according to claim 4 . An information transmission sheet, fiber, cloth, leather, or color filter substrate colored with the azo compound or salt thereof according to any one of claims 1 to 3 .