JP4404308B2 - Water-soluble monoazo compound, ink composition and colored body - Google Patents

Description

  The present invention relates to a water-soluble monoazo compound or a salt thereof, an ink composition containing these, and a colored product obtained using the same.

Among various color recording methods, various ink ejection methods have been developed in ink jet printer recording methods, which are one of the representative methods, all of which generate ink droplets, Recording is performed by adhering to a recording material (paper, film, fabric, etc.). In this method, since the recording head and the recording material do not come into contact with each other, there is no sound generation and it is quiet, and it has been rapidly spreading in recent years due to the features of miniaturization, high speed, and easy colorization. Both are expected to grow significantly.
Conventionally, inks such as fountain pens and felt pens and inks for ink-jet recording have been inks in which water-soluble dyes are dissolved in an aqueous medium. In these water-soluble inks, inks at the pen tip and ink discharge nozzles are used. In general, a water-soluble organic solvent is added to prevent clogging. In these conventional inks, a recording image with sufficient density is provided, the clogging of the pen tip and the nozzle does not occur, the drying property on the recording material is good, the bleeding is small, and the storage stability. In addition, the formed image is required to have fastness such as water resistance, moisture resistance and light resistance.

On the other hand, in order to record image or character information on a color display of a computer with an ink-jet printer, generally four colors of ink of yellow (Y), magenta (M), cyan (C), and black (K) are used. It is expressed by subtractive color mixing. In order to reproduce the additive color mixture image with red (R), green (G), and blue (B) in a CRT display etc. as faithfully as possible with the subtractive color mixture image, each of the dyes used, especially Y, M, and C, It is desired to have a hue close to standard and to be clear. Furthermore, the ink composition is required to be stable against long-term storage, to have a high density of printed images, and to be excellent in fastness such as water resistance, moisture resistance, light resistance and gas resistance. . Gas resistance refers to resistance to a phenomenon in which ozone gas or the like having an oxidizing action existing in the air reacts with a dye on or in a recording paper to cause the printed image to discolor. Ozone gas is considered as a main causative substance that promotes the fading phenomenon of ink jet recorded images. Since this color fading phenomenon is characteristic of ink jet images, improvement of ozone gas resistance is an important issue. In particular, the ink-receiving layer provided on the surface of photographic image-dedicated inkjet paper often uses porous white inorganic materials in order to speed up ink drying and reduce bleeding at high image quality. Discoloration due to ozone gas is noticeable on a fresh recording paper. With the recent spread of digital cameras, there are increasing opportunities to print images at home, and discoloration of images due to oxidizing gas in the air is regarded as a problem when storing the obtained printed matter.
Examples of yellow dye skeletons for inkjet having excellent water solubility and sharpness include C.I. represented by the following formula (5) of a pyrazolone azo compound. I. Acid Yellow 23 (see, for example, Patent Documents 1 to 4) or those proposed in Patent Document 4 are all mentioned, but all of hue, sharpness, light resistance, water resistance, moisture resistance, gas resistance and dissolution stability Nothing that satisfies the requirements has been obtained. Moreover, although the compound similar to the compound of this invention is described in patent document 5, there is no description about the inkjet use and the said performance suitable for it.

JP 2000-178492 4 pages JP-A-2002-241648, pages 2 to 4 Example 1 3 pages of JP2002-53780 JP-A-2002-226739, pages 7 to 8 Examples 1 to 3 JP-A-2003-286420 1-2 pages Examples 1-3 British Patent No. 755550, pages 7-8

  The present invention is a water-soluble dye (compound) having a high solubility in water, a hue and sharpness suitable for ink jet recording, and excellent water resistance, moisture resistance, light resistance and gas fastness of recorded matter, and the same An object of the present invention is to provide an ink composition containing

（式（１）中、Ｒ₁は水素原子または炭素数１〜３のアルキル基を、Ｙ₁はカルボキシル基、メチル基またはフェニル基を、Ｙ₂はヒドロキシル基またはアミノ基をそれぞれ表す。Ｙ₃、Ｙ₄及びＹ₅はそれぞれ独立して水素原子、スルホン酸基またはカルボキシル基を表し、かつＹ₃、Ｙ₄、Ｙ₅のうち少なくとも１つはスルホン酸基又はカルボキシル基である。）
（２）式（１）中のＲ₁が水素原子またはメチル基、Ｙ₁がカルボキシル基、Ｙ₂がヒドロキシル基、Ｙ₃がスルホン酸基で、かつその位置が４位、Ｙ₄及びＹ₅がそれぞれ水素原子である（１）に記載の水溶性モノアゾ化合物又はその塩、
（３）色素成分として、（１）または（２）に記載の水溶性モノアゾ化合物またはその塩を含有することを特徴とするインク組成物、
（４）水溶性有機溶剤を含有する（３）に記載のインク組成物、
（５）インクジェット記録用である（３）または（４）に記載のインク組成物、
（６）インク滴を記録信号に応じて吐出させて被記録材に記録を行うインクジェット記録方法において、インク組成物として（３）から（５）のいずれか一項に記載のインク組成物を用いることを特徴とするインクジェット記録方法、
（７）被記録材が情報伝達用シートである（６）に記載のインクジェット記録方法、
（８）情報伝達用シートが多孔性白色無機物を含有したインク受像層を有する用紙である（７）に記載のインクジェット記録方法、
（９）（１）または（２）に記載の水溶性モノアゾ化合物又はその塩、または（３）から（５）のいずれか一項に記載のインク組成物で着色された着色体、
（１０）着色がプリンタによりなされた（９）に記載の着色体、
（１１）（３）から（５）のいずれか一項に記載のインク組成物を含む容器が装填されたインクジェットプリンタ、
に関する As a result of intensive investigations, the present inventors have found that a water-soluble monoazo compound represented by a specific formula and an ink composition containing the same solve the above-described problems. It has been completed.
That is, the present invention provides (1) a water-soluble monoazo compound represented by the following formula (1) or a salt thereof,

(In the formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y ₁ represents a carboxyl group, a methyl group or a phenyl group, and Y ₂ represents a hydroxyl group or an amino group. Y ₃ Y ₄ and Y ₅ each independently represents a hydrogen atom, a sulfonic acid group or a carboxyl group, and at least one of Y ₃ , Y ₄ and Y ₅ is a sulfonic acid group or a carboxyl group.
(2) In formula (1), R ₁ is a hydrogen atom or a methyl group, Y ₁ is a carboxyl group, Y ₂ is a hydroxyl group, Y ₃ is a sulfonic acid group, and its position is at the 4-position, Y ₄ and Y ₅ Are each a hydrogen atom, the water-soluble monoazo compound or a salt thereof according to (1),
(3) An ink composition comprising the water-soluble monoazo compound or a salt thereof according to (1) or (2) as a dye component,
(4) The ink composition according to (3), which contains a water-soluble organic solvent,
(5) The ink composition according to (3) or (4), which is for inkjet recording.
(6) In an ink jet recording method in which ink droplets are ejected according to a recording signal and recording is performed on a recording material, the ink composition according to any one of (3) to (5) is used as the ink composition. An ink jet recording method,
(7) The inkjet recording method according to (6), wherein the recording material is an information transmission sheet,
(8) The ink jet recording method according to (7), wherein the information transmission sheet is a sheet having an ink image-receiving layer containing a porous white inorganic substance,
(9) A colored body colored with the water-soluble monoazo compound or a salt thereof according to (1) or (2), or the ink composition according to any one of (3) to (5),
(10) The colored product according to (9), wherein coloring is performed by a printer,
(11) An inkjet printer loaded with a container containing the ink composition according to any one of (3) to (5),
About

  The water-soluble monoazo compound of formula (1) or a salt thereof according to the present invention has a very clear and light hue on ink jet recording paper, is excellent in water solubility, and is filtered through a membrane filter during the production of an ink composition. It has the characteristic that the property is good. In addition, the ink composition of the present invention using this compound is free from crystal precipitation, physical property change, color change and the like after long-term storage, and has good storage stability. A printed matter using the water-soluble monoazo compound or a salt thereof of the present invention as an ink for ink jet recording has an ideal hue without selecting a recording material (paper, film, etc.), and the hue of a photographic tone color image. Can be reproduced faithfully on paper. Furthermore, even when recording on a recording material coated with a porous white inorganic material on the surface, such as inkjet special paper (film) for photographic image quality, various fastnesses, that is, water resistance, moisture resistance, light resistance, and gas resistance are good. It is excellent in long-term storage stability of photographic-tone recorded images. Therefore, the water-soluble monoazo compound of the formula (1) or a salt thereof is extremely useful as a coloring matter for ink for ink jet recording.

The present invention will be described in detail. In the present invention, unless otherwise specified, the sulfonic acid group and the carboxyl group are represented in the form of a free acid.
The water-soluble monoazo compound of the present invention is represented by the following formula (1) in the form of a free acid.

（式（１）中、Ｒ₁は水素原子、炭素数１〜３のアルキル基を表わす。Ｙ₁はカルボキシル基、メチル基またはフェニル基をＹ₂はヒドロキシル基またはアミノ基を表す。Ｙ₃ 、Ｙ₄及びＹ₅はそれぞれ独立して水素原子、スルホン酸基、カルボキシル基を表し、かつＹ₃、Ｙ₄、Ｙ₅のうち少なくとも１つはスルホン酸基又はカルボキシル基を含む。）

(In Formula (1), R ₁ represents a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, Y ₁ represents a carboxyl group, a methyl group or a phenyl group, Y ₂ represents a hydroxyl group or an amino group, Y ₃ , Y ₄ and Y ₅ each independently represent a hydrogen atom, a sulfonic acid group, or a carboxyl group, and at least one of Y ₃ , Y ₄ , and Y ₅ contains a sulfonic acid group or a carboxyl group.

The alkyl group having 1 to 3 carbon atoms in R ₁ of formula (1), a methyl group, an ethyl group, n- propyl group, and iso- propyl group is preferably a methyl group.
A particularly preferred combination of R ₁ , Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y _{5 in} the formula (1) is such that R ₁ is a hydrogen atom or a methyl group, Y ₁ is a carboxyl group, and Y ₂ is a hydroxyl group. This is a case where Y ₃ is a sulfonic acid group and the position is at the 4-position, and Y ₄ and Y ₅ are each a hydrogen atom.

  The salt of the compound of formula (1) is an inorganic or organic cation salt. The salt is a lithium salt, a sodium salt, a potassium salt, or an ammonium salt represented by the general formula (2).

(In formula (2), X _{1 to} X ₄ each independently represents a hydrogen atom, an alkyl group, a hydroxyalkyl group or a hydroxyalkoxyalkyl group.)
Examples of the alkyl group in X _{1 to} X ₄ in the formula (2) include a methyl group and an ethyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, 2- Examples thereof include hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxybutyl group, and examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl group, 2-hydroxyethoxyethyl group, 3-hydroxybutyl group, Examples thereof include a hydroxyethoxypropyl group, a 3-hydroxyethoxybutyl group, and a 2-hydroxyethoxybutyl group.

  Among these, preferred are sodium salt, potassium salt, lithium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, triisopropanolamine salt, ammonium salt and the like. It is done. Of these, lithium salts and sodium salts are particularly preferred.

  The above-mentioned salt can be obtained, for example, by adding sodium chloride to a reaction solution, wet cake or dry product dissolved in water, salting out, and filtering to obtain a sodium salt as a wet cake. In addition, if the wet cake is dissolved again in water and then the crystals obtained by adding hydrochloric acid to adjust the pH to 1 to 2 are filtered, the crystals can be obtained in the form of free acid (or partly as sodium salt). Can do. Furthermore, while the wet cake of the free acid is stirred with water, for example, potassium hydroxide, lithium hydroxide, ammonia water or a hydroxide of formula (2) is added to make it alkaline, so that each corresponding potassium Salts, lithium salts, ammonium salts and quaternary ammonium salts are obtained. Of these salts, particularly preferred are lithium and sodium salts.

  The compound represented by the formula (1) of the present invention can be produced, for example, as follows. That is, by an ordinary method, an aromatic amine represented by the following formula (A) is diazotized, and a coupler represented by the following formula (B) and a room temperature (usually 20 to 25 ° C.) and weakly alkaline (usually pH 8 to 9). It can be obtained by a coupling reaction.

Next, preferred examples of the compound represented by the general formula (1) are not particularly limited, but specific examples are listed in Table 1. In Table 1, Ph represents a phenyl group, and the numbers in () in Y _{3 to} Y ₅ in the table represent the substitution position when the substitution position with pyrazole is 1 in the phenyl group.

The water-soluble monoazo compound of the present invention is suitable for dyeing natural and synthetic fiber materials or blended products, and these compounds are suitable for the production of inks for writing and ink jet recording.
The reaction liquid containing the water-soluble monoazo compound of the formula (1) of the present invention can be directly used for the production of an ink composition. However, it can also be isolated from the reaction liquid, dried, for example spray dried, and then processed into an ink composition. The recording ink composition of the present invention contains the compound of the present invention in an aqueous solution usually in an amount of 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass. In the ink composition of the present invention, the water-soluble organic solvent is usually contained in an amount of 0 to 30% by mass, and the ink preparation agent is usually contained in an amount of 0 to 5% by mass.

Specific examples of water-soluble organic solvents that can be used in the ink composition of the present invention include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol. , Carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetamide, lactams such as 2-pyrrolidone and N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3 -Cyclic ureas such as dimethylhexahydropyrimido-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- or 1,3-propylene rubber (C2-, such as coal, 1,2- or 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. C6) Monomer having an alkylene unit, oligomer or polyalkylene glycol or thioglycol, glycerin, polyol (triol) such as hexane-1.2.6-triol, ethylene glycol 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 Polyhydric alcohols (C1 -C4) alkyl ethers such as Le, gamma-butyrolactone or dimethyl sulfoxide and the like. These water-soluble organic solvents are used alone or in combination.
Among these, preferred are 2-pyrrolidone, N-methyl-2-pyrrolidone, mono, di or triethylene glycol, and dipropylene glycol, and more preferred are 2-pyrrolidone, N-methyl-2-pyrrolidone, and diethylene glycol. .

  Examples of the ink preparation agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye dissolving agents, and surfactants. Examples of the antiseptic / antifungal agent include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzthiazole, nitrityl, pyridine, 8- Oxyquinoline, benzothiazole, isothiazoline, dithiol, pyridine oxydide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, Examples thereof include brominated indanone compounds, benzyl bromoacetate compounds, and inorganic salt compounds. 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 in the range of usually 7.0 to 11.0 without adversely affecting the prepared ink. For example, alkanolamines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. And carbonates. Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate and the like. Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone or sulfonated benzotriazole. Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines. Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like. Examples of the surfactant include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant. Examples of anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxyalkyl ethers 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, alkyl allyl sulfone hydrochloride, diethyl sulfosuccinate And dioctyl sulfosuccinate of diethylhexylsilsulfosuccinate. 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 octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ethers such as alkyl ether and polyoxyallylalkyl alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearic acid ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioxide Esters such as oleate, polyoxyethylene monooleate, polyoxyethylene stearate, 2, 4, 7 Acetylene glycol systems such as 9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol (for example, , Surfinol 104, 104PG50, 82, 465, Orphine STG, etc., manufactured by Nissin Chemical Co., Ltd.). These ink preparation agents are used alone or in combination.

The ink composition of the present invention can be produced by dissolving the compound represented by the formula (1) in water and / or a water-soluble organic solvent together with the ink preparation agent and the like.
When the reaction liquid of the compound of the formula (1) is used directly in the production of the ink composition, it is preferable to use one having a low content of inorganic substances such as metal cation chlorides and sulfates. Is about 1% by mass or less. In order to produce a pigment with a small amount of inorganic matter, for example, a desalting treatment may be performed by a method using a reverse osmosis membrane.

  In the said manufacturing method, there is no restriction | limiting in particular in the order which dissolves each component. The compound represented by the formula (1) may be dissolved in water and / or a water-soluble organic solvent in advance, and the ink preparation agent may be added and dissolved, or the compound represented by the formula (1) may be dissolved in water. Thereafter, a water-soluble organic solvent and an ink preparation agent may be added and dissolved. The order may be different from this, and a water-soluble organic solvent and an ink preparation agent are added to a reaction solution of the compound represented by the formula (1) or a solution subjected to a desalting treatment with a reverse osmosis membrane. An ink composition may be produced. In preparing the ink composition of the present invention, the water used is preferably one having few impurities such as ion-exchanged water or distilled water. Furthermore, if necessary, fine filtration may be performed using a membrane filter to remove impurities, and when using as ink for an ink jet printer, it is preferable to perform fine filtration. The pore diameter of the filter for performing microfiltration is usually 1 to 0.1 microns, preferably 0.8 to 0.2 microns.

  The ink composition containing the water-soluble monoazo compound of the present invention is suitable for use in printing, copying, marking, writing, drawing, stamping, or recording methods, particularly ink jet recording. In this case, a high quality yellow print with good resistance to water, sunlight, ozone and friction is obtained.

  The colored body of the present invention is colored with the compound of the present invention. The material to be colored is not particularly limited, and examples thereof include, but are not limited to, paper, fiber and cloth (cellulose, nylon, wool, etc.), leather, and a color filter base material. Examples of the coloring method include a dip dyeing method, a textile printing method, a printing method such as screen printing, a method using an ink jet printer, and the like, and a method using an ink jet printer is preferable.

Some ink jet printers are set with two types of ink, a high-density ink and a low-density ink, for the purpose of supplying a high-definition image. In that case, a high-concentration ink and a low-concentration ink are produced using the compound represented by the formula (1) of the present invention, and the ink set can be used in combination. Moreover, you may use the ink containing the compound represented by Formula (1) only in either one.
Moreover, you may use together the compound represented by Formula (1) of this invention with a well-known yellow pigment | dye. Further, the compound represented by the formula (1) can be used for adjusting the hue of other colors, for example, a black dye, or for mixing with a magenta dye or a cyan dye to adjust a red ink or a green ink. .

  Examples of the recording material (media) to which the ink jet recording method of the present invention can be applied include information transmission sheets such as paper and film, fibers and leather. The information transmission sheet is preferably a surface-treated sheet, specifically, an ink receiving layer provided on these substrates. The ink receiving layer is formed by, for example, impregnating or coating the above-mentioned base material with a cationic polymer, or by converting a porous white inorganic substance capable of absorbing a pigment in ink such as porous silica, alumina sol, or special ceramics to polyvinyl alcohol or polyvinylpyrrolidone. It is provided by coating on the surface of the substrate together with a hydrophilic polymer such as. A paper provided with such an ink receiving layer is usually called an inkjet exclusive paper (film) or glossy paper (film). For example, Pictorico (manufactured by Asahi Glass Co., Ltd.), color BJ paper, color BJ photo film sheet, professional photo Paper (all manufactured by Canon Inc.), color image jet paper (manufactured by Sharp Corporation), PM photo paper, Superfine gloss film (all manufactured by Epson Corporation), Pictafine (Hitachi Maxell Corporation) Etc.) and are commercially available. Of course, it can also be used for plain paper.

  Among these, it is known that an image recorded on a recording material coated with a porous white inorganic substance on the surface is particularly prone to fading by ozone gas, but the ink composition of the present invention has excellent gas resistance. Therefore, it is particularly effective when recording on such a recording material.

  In order to record on the recording material by the ink jet recording method of the present invention, for example, a container containing the above ink composition may be set at a predetermined position of the ink jet printer and recorded on the recording material by a normal method. . In the ink jet recording method of the present invention, the water-based yellow ink composition of the present invention, a publicly known magenta ink composition, a cyan ink composition, a green ink composition, a blue (or violet) ink composition, and a red as necessary. Used in combination with an ink composition, a black ink composition, and the like. The ink composition of each color is injected into each container, and the container is used by being loaded into a predetermined position of the ink jet printer in the same manner as the container containing the aqueous yellow ink composition for ink jet recording of the present invention. Examples of the ink jet printer include a piezo printer using mechanical vibration and a bubble jet (registered trademark) printer using bubbles generated by heating.

  The ink composition of the present invention has a clear yellow color, particularly high clarity on inkjet glossy paper, and has a hue suitable for inkjet recording. In addition, the fastness of the recorded image is very high.

  The ink composition of the present invention does not precipitate or separate during storage. Further, when the ink composition of the present invention is used in ink jet recording, the ejector (ink head) is not blocked. The ink according to the present invention does not cause changes in physical properties even under constant recirculation for a relatively long time by a continuous ink jet printer or intermittent use by an on-demand ink jet printer.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the text, “parts” and “%” are based on mass unless otherwise specified.

Example 1 (Synthesis of Compound No. 1)
21.6 parts of 2-amino-benzoic acid-5-sulfonamide were dissolved in 400 parts of water and 7.2 parts of sodium nitrite were added. This solution was added dropwise to 255 parts of 5% hydrochloric acid at 5 to 10 ° C. over 1 hour, followed by stirring at 10 ° C. or less for 1 hour to carry out a diazotization reaction. A solution obtained by suspending 28.4 parts of 1-p-sulfophenyl-5-pyrazolone-3-carboxylic acid in 50 parts of water is added to the formed diazonium salt, and the pH is 6 to 7 using a sodium hydroxide solution. It stirred at 5-10 degreeC for 3 hours. After filtering the obtained reaction liquid, the filtrate was completely dried with a hot air dryer (80 ° C.) to obtain 50.0 parts of pigment powder. This pigment powder was put into 200 parts of water and 450 parts of methanol, stirred for 1 hour and then filtered. The obtained wet cake was completely dried with a hot air dryer (80 ° C.) to obtain 45.0 parts of a compound represented by the formula (3) (λmax 408 nm in water).

Example 2 (Synthesis of Compound No. 2)
23.0 parts of 2-amino-benzoic acid-5-N-methylsulfonamide were dissolved in 400 parts of water, and 7.2 parts of sodium nitrite was added. This solution was added dropwise to 255 parts of 5% hydrochloric acid at 5 to 10 ° C. over 1 hour, followed by stirring at 10 ° C. or less for 1 hour to carry out a diazotization reaction. A solution obtained by suspending 28.4 parts of 1-p-sulfophenyl-5-pyrazolone-3-carboxylic acid in 50 parts of water is added to the formed diazonium salt, and the pH is 6 to 7 using a sodium hydroxide solution. It stirred at 5-10 degreeC for 3 hours. After filtration of the resulting reaction solution, the filtrate was completely dried with a hot air dryer (80 ° C.) to obtain 52.0 parts of pigment powder. This pigment powder was put into 200 parts of water and 450 parts of methanol, stirred for 1 hour and then filtered. The obtained wet cake was completely dried with a hot air dryer (80 ° C.) to obtain 46.3 parts of a compound represented by the formula (4) (λmax 408 nm in water).

Example 3
(A) Preparation of ink A liquid having the composition shown in Table 2 was prepared using each of the compounds obtained in Examples 1 and 2 and filtered through a 0.45 μm membrane filter. I got a thing. The water used was ion exchange water. Water and ammonia water were added so that the pH of the ink composition was pH = 8-9 and the total amount was 100 parts. Tests using the compounds obtained in Example 1 and Example 2 are referred to as Example 4 and Example 5, respectively.

Table 2 (Preparation of ink composition)
Compound of Example 1 or Example 3.0 parts 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 Surfynol 104PG50 (Manufactured by Nissin Chemical) 0.1 parts water + ammonia water 77.9 parts total 100.0 parts

As a comparison object, C.I. represented by the following formula (5), which is similar to the compound of the formula (1) of the present invention and is widely used as a yellow dye for inkjet, is used. I. An ink was prepared from Acid Yellow 23 with the composition shown in Table 3 in the same manner as in Examples 4 and 5. The test obtained with the obtained ink composition is referred to as Comparative Example 1.

Table 3 (Preparation of ink composition)
C. I. Acid Yellow 23 3.0 parts 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 Surfynol 104PG50 (manufactured by Nisshin Chemical Co., Ltd.) ) 0.1 part water + ammonia water 77.9 parts total 100.0 parts

(B) Inkjet printing Using an inkjet printer (Pixus 550i manufactured by Canon Inc.), glossy paper 1 having a dye-receiving layer (Professional Photo Paper PR-101 manufactured by Canon Inc.), glossy paper 2 (Epson PM photographic paper <Glossy) > KA420PSK) was subjected to ink jet recording. During ink jet recording, an image pattern was created so that gradations with several levels of reflection density were obtained, and a yellow printed matter was obtained.
The light resistance test and the ozone resistance test were performed at a portion where the reflection density D value of the printed material before the test was closest to 1. The reflection density was measured using a color measurement system “GRETAG SPM50: manufactured by GRETAG”.

(C) Humidity resistance test of recorded image The test piece printed on glossy paper 1 and glossy paper 2 is left at 50 ° C. and 90% RH for 7 days using a thermo-hygrostat (manufactured by Applied Giken Sangyo Co., Ltd.). The dye bleeding before and after the test was judged visually. The results are shown in Table 4. The evaluation criteria are as follows.
○ There is almost no bleeding of the dye.
△ Some dye bleeding is observed.
X Dye bleed is seen considerably.

Table 4
Moisture resistance
Example 4 (Glossy paper 1)
Example 4 (Glossy paper 2) ○

Example 5 (Glossy paper 1)
Example 5 (Glossy paper 2) ○

Comparative Example 1 (Glossy Paper 1) ×
Comparative Example 1 (Glossy paper 2) ×

From Table 4, it can be seen that Examples 4 and 5 have superior moisture resistance compared to Comparative Example 1, and in particular, glossy paper 2 has significantly better moisture resistance than Comparative Example 1.

(D) Xenon light resistance test of recorded image Using a xenon weatherometer Ci4000 (manufactured by ATLAS), test pieces printed on glossy paper 1 and glossy paper 2 were irradiated for 50 hours at 0.36 W / square meter illumination before and after the test. The residual ratio after the test was determined from the reflection density ratio (the reflection OD value after the test / the reflection OD value before the test × 100).
The results are shown in Table 5.

Table 5
Light resistance (residual rate%)
Example 4 (Glossy Paper 1) 79
Example 4 (Glossy Paper 2) 86

Example 5 (Glossy Paper 1) 68
Example 5 (Glossy Paper 2) 84

Comparative Example 1 (Glossy Paper 1) 66
Comparative Example 1 (Glossy Paper 2) 73

From Table 5, it can be seen that Examples 4 and 5 have a higher survival rate than Comparative Example, and in particular, glossy paper 2 has very high light resistance.

(E) Ozone gas resistance test of recorded images Using ozone weathermeter (manufactured by Suga Test Instruments Co., Ltd.), the test piece printed on glossy paper 1 and glossy paper 2 is used in an environment with an ozone concentration of 40 ppm, humidity of 60% RH, and temperature of 24 ° C. It was left for 3 hours and 6 hours. Table 6 shows the results of the residual ratio after the test.

Table 6
Ozone resistance (residual rate%)
3 hours 6 hours Example 4 (glossy paper 1) 87 80
Example 4 (Glossy paper 2) 87 70

Example 5 (Glossy paper 1) 78 69
Example 5 (Glossy paper 2) 83 77

Comparative Example 1 (Glossy Paper 1) 55 45
Comparative Example 1 (Glossy Paper 2) 44 22

From Table 6, it can be seen that Examples 4 and 5 have a very high residual ratio after ozone exposure compared to Comparative Example 1, and are extremely excellent in ozone gas resistance.

  From Table 4 to Table 6, it can be seen that the ink composition using the water-soluble monoazo compound of the present invention is extremely useful in terms of moisture resistance, light resistance and gas resistance, and is very useful.

Claims (11)

Water-soluble monoazo compound represented by the following formula (1) or a salt thereof

(In the formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y ₁ represents a carboxyl group, a methyl group or a phenyl group, and Y ₂ represents a hydroxyl group or an amino group. Y ₃ Y ₄ and Y ₅ each independently represents a hydrogen atom, a sulfonic acid group or a carboxyl group, and at least one of Y ₃ , Y ₄ and Y ₅ is a sulfonic acid group or a carboxyl group. In formula (1), R ₁ is a hydrogen atom or a methyl group, Y ₁ is a carboxyl group, Y ₂ is a hydroxyl group, Y ₃ is a sulfonic acid group, and its position is at the 4-position, and Y ₄ and Y ₅ are each hydrogen. The water-soluble monoazo compound or a salt thereof according to claim 1, which is an atom. An ink composition comprising the water-soluble monoazo compound or a salt thereof according to claim 1 or 2 as a dye component. The ink composition according to claim 3, comprising a water-soluble organic solvent. The ink composition according to claim 3 or 4, which is for inkjet recording. In an ink jet recording method in which ink droplets are ejected according to a recording signal and recording is performed on a recording material, the ink composition according to any one of claims 3 to 5 is used as the ink composition. Inkjet recording method The inkjet recording method according to claim 6, wherein the recording material is an information transmission sheet. 8. The ink jet recording method according to claim 7, wherein the information transmission sheet is a paper having an ink image receiving layer containing a porous white inorganic substance. A colored product colored with the water-soluble monoazo compound or a salt thereof according to claim 1 or 2, or the ink composition according to any one of claims 3 to 5. The colored body according to claim 9, wherein coloring is performed by a printer. An inkjet printer loaded with a container containing the ink composition according to any one of claims 3 to 5.