Azo compound and ink composition

The present invention relates to novel azo compounds or salts thereof, ink compositions containing them, and colored bodies thereof.

The recording method using an inkjet printer, which is one of the typical methods among various color recording methods, generates small droplets of ink and attaches them to various recording materials (paper, film, cloth, etc.) for recording. It is something to do. Since this method does not come into contact with the recording head and the material to be recorded, it is quiet with less sound generation, and because it is easy to miniaturize and speed up, it has been rapidly becoming popular in recent years and will continue to grow significantly in the future. Expected. Conventionally, as inks such as fountain pens and felt-tip pens and inks for inkjet recording, water-based inks in which a water-soluble dye is dissolved in a water-based medium have been used. In these water-soluble inks, a pen tip or an ink ejection nozzle is used. A water-soluble organic solvent is generally added to prevent clogging of the ink. For this reason, these conventional inks provide a recorded image having a sufficient density, do not cause clogging of the pen tip or nozzle, have good drying property on the material to be recorded, and have little bleeding. Excellent storage stability and the like are required, and particularly high solubility in water and high solubility in a water-soluble organic solvent added to the ink are required. If the solubility in water or a water-soluble organic solvent is low, a bronzing phenomenon (a phenomenon in which the surface of glossy paper glare like a metal due to the association of pigments) occurs and the print quality is significantly deteriorated. 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 is also called ozone resistance or gas resistance, and is resistant to the phenomenon that ozone gas having an oxidizing action existing in the air acts on the dye in the recording paper and discolors and fades the printed image. That is. In addition to ozone gas, examples of oxidizing gases having this kind of action include NOx and SOx. Among these oxidizing gases, ozone gas is the main cause of further promoting the discoloration and fading phenomenon of inkjet recorded images. It is considered to be a substance. In particular, the ink receiving layer provided on the surface of the photographic image quality inkjet paper uses a porous material such as a white inorganic pigment in order to accelerate the drying of the ink and reduce bleeding in high image quality. On such recording paper, discoloration and fading due to ozone gas are noticeably observed. This is because ozone contained in the air comes into contact with the porous white inorganic silica and alumina contained in the recording paper, and radicals having a strong oxidizing action are generated, which act on the dye to cause discoloration and fading. It seems to be. Since this discoloration / fading phenomenon due to the oxidizing gas is characteristic of inkjet images, improving ozone gas resistance is one of the most important issues in inkjet recording.

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

With the spread of the inkjet recording method, the applications are expanding. Until now, it was generally three colors of yellow, magenta, and cyan, or four colors including black, but the use of multicolor inks such as red, green, blue, and orange is being considered. That is, the challenge of faithfully reproducing all colors in the natural world continues. In order to meet this demand, various dyes and inks that can reproduce all hues, sharpnesses, and densities are required. Further, there is a demand for dyes for yellow to red components for toning to form high-quality black to gray achromatic colors. As a dye for adjusting a yellow to orange dye to a black dye, for example, there is a dye having the following formula (4) that can be produced by the method described in Patent Document 1, and this is a product that fully satisfies the market demand. Not yet provided.

<chemistry num="1"><img file="JP2005298636A_D0001.tif" /></chemistry>

<patcit num="1"><text>Tokukousho 33-7643 Gazette</text></patcit>

<p> 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 a high density of a printed image, does not cause bronzing, and prints. It is an object of the present invention to provide a recorded image having excellent fastness, particularly ozone gas resistance, and to provide a yellow to red ink dye and an ink composition thereof, which are easy to synthesize.</p>

<p> As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific azo dye solves the above-mentioned problems, and have reached the present invention.</p><p> That is, the present invention (1) is an azo compound represented by the following formula (1) or a salt thereof.</p><p><chemistry num="2"><img file="JP2005298636A_D0002.tif" /></chemistry></p><p>(In equation (1), R¹May be substituted with a hydrogen atom; hydroxyl group; carboxyl group; hydroxyl group or (C1 to C4) alkoxy group; (C1 to C4) alkyl group; hydroxyl group or (C1 to C4) alkoxy group. May be (C1 to C4) alkoxy groups; may be substituted with hydroxyl or (C1 to C4) alkoxy groups; (C1 to C4) alkylamino groups; carboxy- (C1 to C5) alkylamino groups; bis- [ Carboxy- (C1 ~ C5) alkyl] amino group; may be substituted with a hydroxyl group or (C1 ~ C4) alkoxy group (C1 ~ C4) alkanoylamino group; substituted with a carboxyl group, sulfo group or amino group May be a phenylamino group; a sulfo group (-SO)₃H); Halogen atom or ureido group, A is an aliphatic or aromatic amine residue or hydroxyl group which may have a substituent, B is an aliphatic or aromatic amine residue which may have a substituent. Represents a group or a residue of a mono or disazo compound, respectively. (2) The azo compound or salt thereof according to (1), wherein A is an aliphatic amine residue or a hydroxyl group having a carboxyl group or a sulfoic 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,</p><p><chemistry num="3"><img file="JP2005298636A_D0003.tif" /></chemistry></p><p>(In equation (2), R¹Represents the same meaning as in the formula (1), and A'represents an aliphatic amine residue or a hydroxyl group having a carboxyl group or a sulfonic acid group, respectively. ) (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). ,</p><p><chemistry num="4"><img file="JP2005298636A_D0004.tif" /></chemistry></p><p>(In equation (3), Z¹, Z², Z³, Z⁴Independently represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a hydroxyalkoxyalkyl group, respectively. ) (5) Use the ink composition according to any one of (1) to (4) or a salt thereof, and the ink composition according to (6) and (5). (7) The inkjet recording method according to (6), wherein the material to be recorded in the inkjet recording method is an information transmission sheet, and (8) the information transmission sheet contains a porous white inorganic substance. The inkjet recording method according to (7), the inkjet printer loaded with the ink composition according to (9) and (5), and any one of (10), (1) to (4). With respect to a colored body colored with an azo compound or a salt thereof.</p>

<p> Since the azo compound of the present invention has excellent water solubility, it has good filterability by a membrane filter in the process of manufacturing an ink composition, and is also excellent in stability during storage of a recording liquid and ejection stability. Further, the ink composition of the present invention containing this azo compound has good storage stability without crystal precipitation, physical characteristic change, color change, etc. after long-term storage. Further, the ink composition containing the azo compound of the present invention is used for inkjet recording and writing tools, and has a high print density of recorded images when recorded on plain paper and inkjet paper, and has gloss used for photographic recording. Bronzing does not occur even with paper. Furthermore, when used in combination with magenta, cyan, and yellow dyes, which have excellent fastness, especially ozone gas resistance, full-color inkjet recording with a wide range of colors and excellent fastness is possible. As described above, the azo compound of the present invention is useful as a dye for obtaining a wide range of hues from yellow to red, or as a dye for adjusting a slight difference in color tone (dye for toning), and an ink as a preferable form. It is prepared into a composition and used for use.</p>

Hereinafter, the present invention will be described in detail.

In the compound of formula (1) of the present invention, R₁Is substituted with a hydrogen atom; hydroxyl group; carboxyl group; hydroxyl group or (C1 to C4) alkyl group; (C1 to C4) alkyl group; hydroxyl group or (C1 to C4) alkoxy group. May be (C1 to C4) alkoxy group; may be substituted with a hydroxyl group or (C1 to C4) alkoxy group (C1 to C4) alkylamino group; carboxy- (C1 to C5) alkylamino group; bis- [ Carboxy- (C1 ~ C5) alkyl] amino group; may be substituted with a hydroxyl group or (C1 ~ C4) alkoxy group (C1 ~ C4) alkanoylamino group; phenyl group is carboxyl group, sulfo group or amino group A phenylamino group which may be substituted; a sulfo group; a halogen atom or a ureido group, A has an aliphatic or aromatic amine residue or a hydroxyl group which may have a substituent, and B has a substituent. The residues of the aliphatic or aromatic amine or the residue of the mono or disazo compound which may be used are shown, respectively.

In the above, specific examples of the (C1 to C4) alkyl group which may be substituted with a hydroxyl group or a (C1 to 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. Further, examples of the (C1 to C4) alkoxy group which may be substituted with a hydroxyl group or a (C1 to C4) alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and the like. tert-butoxy, 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, Examples thereof include isopropoxybutoxy, n-propoxybutoxy, 2-hydroxyethoxyethoxy and the like. Furthermore, examples of (C1 to C4) alkylamino groups that may be substituted with hydroxyl groups or (C1 to C4) alkoxy groups 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 can be mentioned. Further, examples of the carboxy- (C1 to C5) alkylamino group include carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxy-n-butylamino, carboxy-n-pentylamino and the like. Further, examples of the bis- [carboxy- (C1 to C5) alkyl] amino group include bis- (carboxymethyl) amino, bis- (carboxyethyl) amino, bis- (carboxypropyl) amino and the like. Further, examples of the (C1 to C4) alkanoylamino group which may be substituted with a hydroxyl group or a (C1 to 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 can be mentioned. Furthermore, examples of phenylamino groups 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 and diaminophenyl. Amino, diaminosulfophenylamino and the like can be mentioned. Furthermore, specific examples of aliphatic amine residues that may have a substituent include sulfomethylamino, sulfoethylamino, 2-sulfopropylamino, 3-sulfopropylamino, sulfo-n-butylamino, and 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 and the like can be mentioned. Further, specific examples of aromatic amino residues that 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. Further, the mono or disazo compound is preferably appropriately selected from the residues of the monoazo compound or disazo compound having a hydrophilic group such as a carboxyl group or a sulfo group and having an amino group.

Of these, the preferred one is R₁For, 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 a disuazo compound represented by the formula (7) described later. The group (-NH) is preferable, and more preferable groups include the groups shown in Tables 1 and 2 ((1) to (3)) described later.

The azo compound of the present invention represented by the general formulas (1) and (2) can be synthesized by, for example, 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 here. The structural formula of each compound shall be expressed in the form of free acid. That is, equation (5)

<chemistry num="5"><img file="JP2005298636A_D0005.tif" /></chemistry>

The compound represented by is diazotized by a conventional method, and the formula (6)

<chemistry num="6"><img file="JP2005298636A_D0006.tif" /></chemistry>

Equation (7) generated by coupling reaction with the compound represented by

<chemistry num="7"><img file="JP2005298636A_D0007.tif" /></chemistry>

Cyanur chloride is reacted with the compound represented by the formula (8) to obtain the compound represented by the formula (8).

<chemistry num="8"><img file="JP2005298636A_D0008.tif" /></chemistry>

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

<chemistry num="9"><img file="JP2005298636A_D0009.tif" /></chemistry>

Obtain the compound represented by. Under alkaline conditions, the above-mentioned aliphatic amine having a carboxyl group or a sulfo group (corresponding to A) is added and condensed to obtain a compound represented by the formula (2).

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

<tables num="1"><img file="JP2005298636A_D0010.tif" /></tables>

Preferable examples of residues of mono-disazo compounds include the following groups.

<tables num="2"><img file="JP2005298636A_D0011.tif" /></tables>

<tables num="3"><img file="JP2005298636A_D0012.tif" /></tables>

<tables num="4"><img file="JP2005298636A_D0013.tif" /></tables>

The diazotization of the compound of formula (5) is carried out by a method known per se, for example in an inorganic acid medium, for example at a temperature of -5 to 40 ° C, preferably 5 to 25 ° C, for nitrite, for example sodium nitrite. It is carried out using an alkali metal nitrite such as. Coupling of the diazodized 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 at a temperature of, for example, -5 to 30 ° C, preferably 5 to 20 ° C and an acidic to neutral pH value. It is preferably carried out at a weakly acidic to neutral pH value, for example pH 2-6. This pH value adjustment is carried out by the addition of a base. As the base, for example, 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 can be used. .. The compounds of formulas (5) and (6) are used in stoichiometric quantities.

The reaction of the compound of formula (7) with cyanur 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 0-40 ° C, preferably 0-30 ° C and at pH 1-7, preferably pH 3-7. The compound of formula (7) and cyanuric chloride are used in stoichiometric quantities.

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 at a pH of 3-10, preferably pH 6-8. The compounds of formulas (7) and (8) are used in stoichiometric quantities.

The reaction of the compound of formula (9) with an aliphatic amine having an arbitrary 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 at pH 5-13, preferably pH 6-11. The compound of formula (9) and any aliphatic amine are used at a ratio of 1: 1.5 to 3.0.

Azo compounds represented by the general formula (1) or (2) according to the present invention or salts thereof (hereinafter, unless otherwise specified, compounds of the general formulas (1) and (2) or salts thereof are collectively referred to as "compounds of the present invention". After the coupling reaction, it can be isolated in the form of free acid by adding mineral acid, and the inorganic salt can be removed 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 corresponding salt solution. Examples of inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, and alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate. Examples of organic bases include organic amine salts and alkanolamine salts. Preferred amine salts include salts represented by the above formula (3). In the salt represented by equation (3), Z¹, Z², Z³And Z⁴Independently represents a hydrogen atom, an alkyl group, a hydroxyalkyl group or a hydroxyalkoxyalkyl group. Where Z¹, Z², Z³And Z⁴Specific examples of the above are hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxy. Propyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxybutyl group, hydroxyethoxymethyl group, 2-hydroxyethoxyethyl group, 3-hydroxyethoxypropyl group, 2-hydroxyethoxypropyl group, 4-hydroxy Examples thereof include an ethoxybutyl group, a 3-hydroxyethoxybutyl group and a 2-hydroxyethoxybutyl group.

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

The reaction solution containing the compound of the present invention can be directly used in the production of a recording ink composition. However, it is first dried, for example, spray dried and isolated, salted with inorganic salts such as sodium chloride, potassium chloride, calcium chloride and sodium sulfate, or acidified with mineral acids such as hydrochloric acid, sulfuric acid and nitrate. Alternatively, the azo compound of the present invention can be taken out by acid separation by combining the above-mentioned salt analysis and acid analysis, and then processed into an ink composition.

The ink composition of the present invention is a composition mainly containing water containing the compound of the present invention in an amount of usually 0.1 to 20% by mass, preferably 1 to 10% by mass, and more preferably 2 to 8% by mass. 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. The pH of the ink composition is preferably pH 6 to 10, more preferably pH 7 to 10, for the purpose of improving storage stability. The surface tension of the ink composition is preferably 25 to 70 mN / m, more preferably 25 to 60 mN / m. Further, the viscosity of the ink composition is preferably 30 mPa · s or less, more preferably 20 mPa · s or less.

The water-based 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 inkjet printer, it is preferable to use a compound of the present invention having a low content of inorganic substances such as chlorides and sulfates of metal cations, and a guideline for the content thereof. Is, for example, about 1% by mass or less (anti-dye substance). In order to produce the compound of the present invention having a small amount of inorganic substances, for example, the 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. It may be desalted by a method such as

Examples of the water-soluble organic solvent that can be used in the preparation of the ink composition include C1 to C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol, and third 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-dimethylimidazolidine-2-one or 1,3-dimethylhexahydropyrimido. Cyclic ureas such as -2-one, acetone, methyl ethyl ketone, ketone such as 2-methyl-2-hydroxypentane-4-one or keto alcohol, cyclic ether such as tetrahydrofuran and 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 , Polyols having (C2 ~ C6) alkylene units such as thiodiglycol and dithiodiglycol, oligomers or polyalkylene glycols or polyols such as thioglycol, glycerin, hexane-1,2,6-triol (triol), ethylene glycol Polyhydric alcohols such as monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether or triethylene glycol monomethyl ether or triethylene glycol monoethyl ether (C1 to C4) alkyl ethers, γ-butyrolactone or dimethylsulfoxide. And so on. These organic solvents may be used alone or in combination of two or more.

Examples of ink preparations used as necessary in the preparation of the ink composition include, for example, antifungal agents, preservatives, antiseptic antifungal agents, pH adjusters, chelating reagents, rust preventives, and water-soluble ultraviolet absorption. Examples thereof include agents, water-soluble polymer compounds, dye dissolving agents, antioxidants, and surfactants. Specific examples and amounts of each drug that can be used will be described below.

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

Examples of preservatives include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloallyl sulfone-based, iodopropagil-based, N-haloalkylthio-based, benzothiazole-based, nitrile-based, pyridine-based, and 8-oxyquinolin-based. , Benzothiazole-based, isothiazoline-based, dithiol-based, pyridineosidide-based, nitropropane-based, organic tin-based, phenol-based, tetraammonium salt-based, triazine-based, thiazine-based, anilide-based, adamantan-based, dithiocarbamate-based, brominated indanone Examples thereof include compounds such as system, benzyl bromacetate system, and inorganic salt system. Examples of the organic halogen-based compound include pentachlorophenol sodium, examples of the pyridine osoxide-based compound include 2-pyridinethiol-1-oxide sodium, and examples of the inorganic salt-based compound include anhydrous sodium acetate. As isothiazolin-based compounds, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5 -Chloro-2-methyl-4-isothiazolin-3-onemagnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-onecalcium chloride, 2-methyl-4-isothiazolin-3-onecalcium chloride, etc. Can be mentioned. Other antiseptic and fungicides include sodium sorbate, sodium benzoate and the like.

As the pH adjuster, any substance can be used as long as the pH of the ink can be controlled in the range of 5 to 11, for example, without adversely affecting the ink to be blended. 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. , 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 the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetic acid, sodium hydroxyethylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, sodium uracil diacetate and the like. Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglucolate, diisopropylammonium nitrate, pentaerythritol tetranitrate, dicyclohexylammonium nitrate and the like.

Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone compounds, benzotriazol compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds. Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines, polyimines and the like. Examples of the dye dissolving agent include ε-caprolactam, ethylene carbonate, urea and the like.

As the antioxidant, for example, various organic and metal complex-based anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocyclics and the like.

Examples of the surfactant include known surfactants such as anionic, cationic and nonionic surfactants. Anionic surfactants include alkyl sulfonic acid, alkyl carboxylate, α-olefin sulfonate, polyoxyethylene alkyl ether acetate, N-acyl amino acid and its salts, N-acylmethyl taurine salt, alkyl sulfate polyoxy. Alkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, loginate soap, castor oil sulfate, lauryl alcohol sulfate, alkylphenol type phosphoric acid ester, alkyl type phosphoric acid ester, alkylallyl sulfonic acid, diethyl sulfo amber Examples thereof include acid salt, dioctyl sulfo sulfonate, diethyl hexyl sulfo sulfonate. Examples of the cationic surfactant include a 2-vinylpyridine derivative and a poly4-vinylpyridine derivative. Amphoteric tensides include betaine lauryldimethylaminoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amide propyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxyallyl kill. Ethers such as alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monoole Esters such as ate and polyoxyethylene stearate, 2,4,7,9-tetramethyl-5-decine-4,7-diol, 3, Acetylene glycols such as 6-dimethyl-4-octyne-3,6-diol and 3,5-dimethyl-1-hexin-3ol (for example, Surfinol 104, 105, 82, 465, Orfin manufactured by Nissin Chemical Co., Ltd.) (STG, etc.), etc. These ink preparations are used alone or in combination.

The water-based ink composition of the present invention is obtained by mixing and stirring each of 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 narrow substances. Further, in order to prepare an ink composition having a hue of each color, the ink composition may be mixed with other dyes having various hues. That is, in addition to the compound of the present invention, it can be mixed with a compound (dye) of a yellow color, a magenta color, a cyan color, a black color or another color having another hue.

Although the ink composition of the present invention can be used in various fields, it is suitable for water-based writing inks, water-based printing inks, information recording inks, etc., and is used as an inkjet ink containing the ink composition. Is particularly preferable. 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 inkjet recording method of the present invention will be described. The inkjet recording method of the present invention is characterized in that recording is performed using an inkjet ink containing the ink composition. In the inkjet recording method of the present invention, recording is performed on an image receiving material using an inkjet ink containing the ink composition, but the ink nozzle and the like used at that time are not particularly limited and may be used according to the purpose. A known method, for example, a charge control method for ejecting ink using an electrostatic attraction, a drop-on-demand method (pressure pulse method) for using the vibration pressure of a piezo element, and an electric signal can be appropriately selected. An acoustic inkjet method that converts ink into an acoustic beam and irradiates the ink to eject the ink using radiation pressure. A thermal inkjet method that heats the ink to form bubbles 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 by using a plurality of inks having substantially the same hue but different densities, and a colorless and transparent method. A method using ink is included.

The colored body of the present invention is colored with the above-mentioned compound of the present invention or an ink composition containing the same, and more preferably colored with an inkjet printer using the ink composition of the present invention. Examples of those that can be colored include information transmission sheets such as paper and film, fibers and cloths (cellulose, nylon, wool, etc.), leather, and base materials for color filters. As the information transmission sheet, a surface-treated sheet, specifically, a sheet having an ink receiving layer provided on a base material such as paper, synthetic paper, or a film is preferable. In the ink receiving layer, for example, by impregnating or coating the above-mentioned base material with a cationic polymer, or by impregnating or coating a porous white inorganic fine particle such as porous silica, alumina sol, or special ceramics, which can absorb dyes in the ink. It is provided by coating the surface of the base material together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone. Specific examples of porous white inorganic substances used for coating include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopon, and zeolite. , Barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and the like. Those provided with such an ink receiving layer are usually called inkjet paper (film), glossy paper (film), etc. For example, Pictorico (manufactured by Asahi Glass Co., Ltd.), Professional Photo Paper PR-101, Super Photo Paper, etc. Matte photo paper (all manufactured by Canon Corporation), PM photo paper (glossy), PM matte paper (all manufactured by Seiko Epson Corporation), premium plus photo paper, premium glossy film, photo paper (all made by Nippon Hulett) -Commercially available as Photo-like QP (manufactured by Konica Co., Ltd.), etc. (manufactured by Packard Co., Ltd.). Of course, plain paper can also be used.

The compound of the present invention has excellent 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 characteristic change, color change, etc. after long-term storage. Further, the recording ink liquid containing the azo compound of the present invention is used for inkjet recording and writing tools, and has a high print density when recorded on plain paper and inkjet paper, and further has ozone gas resistance, light resistance and moisture resistance. Excellent in sex.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In addition, "part" and "%" in the text are based on weight unless otherwise specified.

Example 1 35.7 parts of the compound of formula (10) was dissolved in 400 parts of water with sodium hydroxide while adjusting the pH to 5.5 to 8.0, and then the temperature was adjusted to 15 to 25 ° C. 18.9 parts of an aqueous sodium nitrate solution was added to diazotize.

<chemistry num="10"><img file="JP2005298636A_D0014.tif" /></chemistry>

24.5 parts of the compound of the formula (11) was added to this diazo solution. 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, and a reaction solution containing the compound of the formula (12) was obtained. Then, sodium chloride was added, salting out was performed, the mixture was filtered, and then dried to obtain 55.2 parts of the monoazo compound of the formula (12).

<chemistry num="11"><img file="JP2005298636A_D0015.tif" /></chemistry>

<chemistry num="12"><img file="JP2005298636A_D0016.tif" /></chemistry>

Next, 27.0 parts of the compound of the formula (12) obtained above was added to 1000 parts of water, the pH was adjusted to 6.0 to 7.0 with liquid caustic soda, and 8.9 parts of cyanuric chloride was added at 10 to 20 ° C. After the addition, the pH was maintained at pH = 6.0 to 7.5 with sodium carbonate, and the mixture was stirred for 2 hours to obtain a solution containing the compound of formula (13).

<chemistry num="13"><img file="JP2005298636A_D0017.tif" /></chemistry>

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

<chemistry num="14"><img file="JP2005298636A_D0018.tif" /></chemistry>

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

<chemistry num="15"><img file="JP2005298636A_D0019.tif" /></chemistry>

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

<chemistry num="16"><img file="JP2005298636A_D0020.tif" /></chemistry>

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

<chemistry num="17"><img file="JP2005298636A_D0021.tif" /></chemistry>

<chemistry num="18"><img file="JP2005298636A_D0022.tif" /></chemistry>

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

<chemistry num="19"><img file="JP2005298636A_D0023.tif" /></chemistry>

<chemistry num="20"><img file="JP2005298636A_D0024.tif" /></chemistry>

Example 5 At the stage of synthesizing the compound of the formula (14) of the first embodiment, the method of the formula (12) is replaced with 14.2 parts of the compound of the formula (21), and the same as the method of the first example. 29.8 parts of the compound of 22) was obtained. The maximum absorption wavelength of this compound in water was 398 nm.

<chemistry num="21"><img file="JP2005298636A_D0025.tif" /></chemistry>

<chemistry num="22"><img file="JP2005298636A_D0026.tif" /></chemistry>

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

<chemistry num="23"><img file="JP2005298636A_D0027.tif" /></chemistry>

<chemistry num="24"><img file="JP2005298636A_D0028.tif" /></chemistry>

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

<chemistry num="25"><img file="JP2005298636A_D0029.tif" /></chemistry>

<chemistry num="26"><img file="JP2005298636A_D0030.tif" /></chemistry>

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

<chemistry num="27"><img file="JP2005298636A_D0031.tif" /></chemistry>

<chemistry num="28"><img file="JP2005298636A_D0032.tif" /></chemistry>

Example 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 the water-based ink composition of the present invention for inkjet. Ion-exchanged water was used as the water. Water and ammonium hydroxide were added so that the pH of the ink composition was pH = 8 to 9.

Table 3 5.0 parts of each compound obtained in the above example (using desalted one) 5.0 parts of glycerin 5.0 parts of urea 5.0 parts of N-methyl-2-pyrrolidone 4.0 parts of isopropyl alcohol 3.0 parts of butyl carbitol 2.0 parts of surfactant 0.1 part (Surfinol 105 manufactured by Nisshin Kagaku Co., Ltd.) Water + ammonium hydroxide aqueous solution 75.9 parts Total 100.0 parts

In Table 3, the compounds obtained in the above Examples include the compound of formula (15) in Example 9, the compound of formula (16) in Example 10, and the compound of 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), and Example 15 is a compound of formula (26). Example 16 shows the compounds of the compound of formula (28), respectively. The pH at the time of ink preparation was adjusted to 8 to 9 with ammonium hydroxide. This water-based ink composition did not undergo precipitation separation during storage and did not change in physical properties even after long-term storage.

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

(C) Evaluation of recorded images The recorded images using the aqueous ink composition of the present invention were evaluated for three points: bronzing, residual concentration after light resistance test, and residual concentration after ozone gas resistance test. The bronzing property and ozone gas resistance tests were performed only on the special glossy paper PR and PM. The results are shown in Table 4. The test method is shown below. (a) The glossy paper for bronzing property was evaluated according to the following criteria by observing the surface of the highest density part. The printed part shows the same glossiness as the non-printed part The printed part has a considerably deteriorated glossy condition compared to the non-printed part × The printed part shows metallic glare and loses the gloss (b) Light resistance test Using a xenon weather meter Ci4000 (manufactured by ATLAS), the printed sample was irradiated with an illuminance of 0.36 W / square meter for 50 hours. After the test was completed, the residual rate of the concentration after the test was measured using the above color measurement system. The judgment was made based on the following. Residual rate: 95% or more Residual rate is less than 95% to 90% or more × Residual rate: Less than 90% (c) Ozone gas resistance test Using an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.), the printed sample was left for 6 hours at an ozone concentration of 40 ppm, a humidity of 60% RH, and a temperature of 24 ° C. After the test was completed, the residual concentration rate after the test was measured using the above color measurement system. The judgment 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 × Residual rate after 6 hours of four houses is less than 70%

Comparative Example 1 As a water-soluble ink jet dye for comparison, an ink composition was prepared with the same ink composition as in Examples 9 to 16 according to the formula (4) that can be produced by the method described in Patent Document 1. Table 4 shows the results of the print density evaluation, light resistance evaluation, and ozone gas resistance evaluation of the obtained recorded image.

<chemistry num="40"><img file="JP2005298636A_D0033.tif" /></chemistry>

Table 4 Bronzing Light resistance Ozone gas resistance Example 9 (Equation (15)) Plain paper --Special glossy paper PR Special glossy paper PM Example 10 (Equation (16)) Plain paper - Dedicated glossy paper PR Dedicated glossy paper PM Example 11 (Equation (18)) Plain paper --Special glossy paper PR Dedicated glossy paper PM Example 12 (Formula (20)) Plain paper --Dedicated glossy paper PR Dedicated glossy paper PM Example 13 (Formula (22)) Plain paper --Dedicated Glossy paper PR Dedicated glossy paper PM Example 14 (Equation (24)) Plain paper --Special glossy paper PR Dedicated glossy paper PM Example 15 (Formula (26)) Plain paper --Dedicated glossy paper PR × Dedicated glossy paper PM Example 16 (Formula (28)) Plain paper --Dedicated Glossy paper PR × Dedicated glossy paper PM Comparative example 1 (Equation (4)) Plain paper × --Special glossy paper PR × × Dedicated glossy paper PM ×

The following can be seen from Table 4. In Comparative Example 1, bronzing occurs on glossy paper due to its low solubility. The product of the present invention has high solubility and no bronzing occurs. The ink composition containing the compound of the present invention has excellent 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 inkjet recording and writing instruments.