JP2013256598A - Ink composition, inkjet printing method and colored matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous orange ink composition having hue and clearness suitable for inkjet printing, and giving orange-color printed images of printed matter excellent in various fastness including moisture resistance, water resistance, light resistance and ozone gas resistance, especially light resistance and ozone gas resistance.SOLUTION: An aqueous orange ink composition is provided, including: as component (I), a compound of formula (1) or a salt thereof; and as component (II), a dye with the λmax (maximum absorption wavelength) determined in its aqueous solution of pH 7 being ≥420 nm and ≤500 nm.

Description

  The present invention relates to an aqueous orange ink composition, an ink jet recording method using the same, and a colored body.

  Various ink ejection methods have been developed as recording methods using an ink jet printer, but all of them generate ink droplets and attach them to various recording materials (paper, film, fabric, etc.) for recording. Is. The recording method using an ink jet printer has a feature that since the recording head and the recording material do not contact with each other, no sound is generated and the recording head is quiet, and printing can be performed at any place such as uneven cotton, a flexible material, and a fragile product. In addition, due to the features that printers can be reduced in size, increased in speed, and easily converted into color, they have rapidly spread in recent years and are expected to grow greatly in the future.

  In order to record image or character information on a color display of a computer with an ink jet printer in color, it is generally subtracted by four colors of ink of yellow (Y), magenta (M), cyan (C), and black (K). Expressed in a mixed color. In order to reproduce additive color mixture images of red (R), green (G), and blue (B) such as CRT displays as faithfully as possible by subtractive color mixture, it is possible to use as much as possible for the dyes used, especially the dyes used for YMC ink. It is desired to have a hue close to the standard of each YMC and to be clear. However, in order to record a photographic image more accurately, only the three primary colors Y, M, and C are insufficient in terms of hue and sharpness. In addition, even when Y, M, and C, which are conventionally used for inkjet, are mixed in advance and inks such as R, G, and B are adjusted and ink jet recording is performed using them, the problem is that the sharpness is still inferior. Remains. Furthermore, the ink composition is required to be stable for long-term storage, to have a high density of printed images, and to be excellent in fastness such as water resistance, light resistance and ozone resistance.

As a method for solving these problems, an ink jet printing method using ink compositions of seven colors (Y, M, C, R, G, B, K) has been proposed. (Patent Document 1) uses a vat dye having a soluble group (patent dye), and in order to completely satisfy market demands in terms of hue, vividness, fastness, etc. Not reached. In Patent Document 1, red (R) ink is used. However, in order to further improve the sharpness of an image, a clearer image can be obtained by using orange (O) instead of red ink. It is known. Further, it is described that an orange direct dye is used as a yellow (Y) ink in an ink jet recording ink set (Patent Document 2).
Further, in inkjet recording, an orange reactive dye is cited as a pigment for orange ink that can form an image having an excellent color gamut (Patent Document 3). However, even with these dyes, hue, sharpness, fastness, storage stability of the ink composition, and the like have not yet satisfied all the market requirements.
Furthermore, in inkjet recording, it is required that the density of a printed image is high and that the fastness such as water resistance, moisture resistance, light resistance and gas resistance is excellent. Gas resistance refers to the resistance to the phenomenon that an oxidizing gas such as ozone gas that exists in the air reacts with a dye on or in the recording paper, causing the printed image to discolor. is there. In particular, ozone gas is regarded as a main causative substance that promotes the fading phenomenon of ink jet recorded images. Since this color fading phenomenon is characteristic of inkjet images, improvement of ozone gas resistance is an important issue. In particular, the ink demand layer provided on the surface of photographic high-quality inkjet dedicated paper often uses porous materials in order to expedite ink drying and reduce bleeding at high image quality. Discoloration due to ozone gas is noticeable on such recording paper. With the recent spread of digital cameras, the opportunity to print images taken at home on recording materials has increased, and when storing the obtained printed matter, discoloration of the image due to oxidizing gas in the air is regarded as a problem. The Moisture resistance refers to the resistance to the phenomenon that the dye in the recording material (or on the recording material) bleeds when the recording material with the printed image is stored in a high humidity atmosphere. It is. When dye bleeding occurs, particularly in an image that requires high-definition image quality such as a photographic tone, the image quality is significantly lowered. Therefore, it is important to reduce such bleeding as much as possible. As described above, moisture resistance is also an important issue required for ink-jet pigments as in the case of ozone gas resistance described above. Furthermore, light resistance is also an important issue in imparting long-term image storage stability. In Patent Document 4, an orange ink composition using only the compound of formula (1) as a dye has high light resistance and clearness. Although it is mentioned as a dye having both properties, in recent years, higher light resistance has been demanded.

Japanese Patent Laid-Open No. 2002-241661 JP 2002-256187 A JP 2003-34765 A Japanese Patent No. 4408734 Kenzo Konishi, Nobuhiko Kuroki “Chemistry of Synthetic Dyes” Tatsumi Shoten March 15, 1965 143-145, 187-188 Hosoda Yutaka "Theoretical Manufacturing Dye Chemistry" Gihodo Co., Ltd. October 1, 1963 190-193

  The present invention is an orange color having hue and sharpness suitable for ink jet recording, and various fastnesses such as moisture resistance, water resistance, light resistance, ozone gas resistance of the recorded matter, and particularly excellent in light resistance and ozone gas resistance. An object of the present invention is to provide a water-based orange ink composition that gives an image of

２）
上記成分（ＩＩ）が、下記式（２）で表される化合物又はその塩である上記１）に記載の水性オレンジインク組成物、

（式（２）において、Ｒ^１はスルホ基又はカルボキシ基を表し、Ｒ^２は（Ｃ１−Ｃ４）アルキル基又は（Ｃ１−Ｃ４）アルコキシ基を表し、Ｒ^３はスルホ基又はカルボキシ基を表す。）
３）
上記式（２）において、Ｒ^１及びＲ^３がスルホ基であり、Ｒ^２がメチル基である上記２）に記載の水性オレンジインク組成物、
４）
上記成分（ＩＩ）が下記式（３）で表される化合物又はその塩である上記１）乃至３）のいずれか一項に記載の水性オレンジインク組成物、

５）
インクジェット記録用である上記１）乃至４）のいずれか一項に記載の水性オレンジインク組成物、
６）
上記１）乃至５）のいずれか一項に記載の水性オレンジインク組成物を含有するインクセット、
７）
少なくともイエロー、マゼンタ、シアン、及び上記１）乃至５）のいずれか一項に記載の水性オレンジインク組成物を含有するオレンジ、の４色を含有する上記６）記載のインクセット、
８）
上記６）又は７）に記載のインクセットを用いることを特徴とするインクジェット記録方法、
９）
被記録材が情報伝達用シートである上記８）に記載のインクジェット記録方法、
１０）
上記１）乃至５）のいずれか一項に記載の水性オレンジインク組成物で着色された着色体、
に関する。 That is, the present invention
1)
A compound represented by the following formula (1) as a component (I) or a salt thereof, and an aqueous orange containing a dye having a λmax (maximum absorption wavelength) measured in an aqueous solution of pH 7 as a component (II) of 420 nm or more and 500 nm or less An ink composition,

2)
The aqueous orange ink composition according to 1), wherein the component (II) is a compound represented by the following formula (2) or a salt thereof:

(In formula (2), ^{R 1} represents a sulfo group or carboxy group, ^{R 2} represents a (C1-C4) alkyl or (C1-C4) alkoxy group, ^{R 3} represents a sulfo group or a carboxy group. )
3)
In the above formula (2), the water-based orange ink composition according to the above 2), wherein R ¹ and R ³ are sulfo groups and R ² is a methyl group,
4)
The aqueous orange ink composition according to any one of 1) to 3), wherein the component (II) is a compound represented by the following formula (3) or a salt thereof:

5)
The water-based orange ink composition according to any one of 1) to 4) above for inkjet recording,
6)
An ink set comprising the aqueous orange ink composition according to any one of 1) to 5) above;
7)
The ink set according to 6) above, which contains at least four colors of yellow, magenta, cyan, and orange containing the aqueous orange ink composition according to any one of 1) to 5) above;
8)
An ink jet recording method using the ink set described in 6) or 7) above;
9)
The inkjet recording method according to 8) above, wherein the recording material is an information transmission sheet,
10)
A colored body colored with the water-based orange ink composition according to any one of 1) to 5) above;
About.

  The water-based orange ink composition of the present invention has the characteristics that the hue is very high on the ink jet recording paper and has good filterability by a membrane filter or the like in the process of producing the ink composition. Furthermore, the aqueous orange ink composition of the present invention has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage. The recorded image obtained using the aqueous orange ink composition of the present invention as an orange ink for ink jet recording has an ideal orange hue without selecting a recording material (paper, film, etc.) It is possible to reproduce a clear orange rather than reproducing the orange color with yellow ink and magenta ink conventionally used for inkjet recording. Furthermore, the water-based orange ink composition of the present invention gives an orange image excellent in various fastnesses such as moisture resistance, water resistance, light resistance and ozone gas resistance, in particular, light resistance and ozone gas resistance.

The present invention will be described in detail below.
In the present specification, unless otherwise specified, acidic functional groups such as sulfo groups and carboxy groups are represented in the form of free acids. Further, the compound contained in the aqueous orange ink composition of the present invention includes a salt thereof and means “a compound and a salt thereof”, but it is complicated to always describe both of them as “a compound or a salt thereof”. Therefore, unless otherwise specified, for the sake of convenience, the term “compound or salt thereof” including both the “compound or its salt” may be simply described as “compound” in the following description.

The aqueous orange ink composition of the present invention contains a compound represented by the above formula (1) as component (I).
This compound can be synthesized, for example, by the methods described in Non-Patent Document 1 and Non-Patent Document 2. In addition, C.I. I. (Color Index) It is also possible to obtain from the market as Direct Orange 39.
When obtained by any of the above methods, what is obtained is not a single substance but a mixture of several compounds. In the aqueous orange ink composition of the present invention, the mixture may be used as it is or may be used after purification, but it is preferable to use it after purification.

The aqueous orange ink composition of the present invention further contains, as component (II), a dye having a λmax (maximum absorption wavelength) measured in an aqueous solution of pH 7 of 420 nm or more and 500 nm or less. By using a dye that satisfies this characteristic, it is possible to express a wide range of hues, achieve high sharpness, and solve the above problems. A more preferable range of λmax is 430 nm or more and 495 nm or less, and particularly preferably 440 nm or more and 490 nm or less.
Examples of the dye satisfying this characteristic include C.I. I. Reactive Orange 13 (λmax = 488 nm), C.I. I. Acid Orange 33 (λmax = 490 nm), C.I. I. Acid Orange 95 (λmax = 490 nm), a compound represented by the above formula (2) (λmax = 453 nm), and the like. Among these, the compound represented by the above formula (2) is particularly preferable. This compound can be synthesized by the method described in Patent Document 4 above. In addition, C.I. I. It is also possible to obtain it as Direct Orange 17 from the market.

In the above formula (2), R ¹ represents a sulfo group or a carboxy group. Of these, a sulfo group is preferred.

In the above formula (2), R ² represents a (C1-C4) alkyl group or a (C1-C4) alkoxy group.
Examples of the (C1-C4) alkyl group include linear or branched ones, but linear ones are preferred. Specific examples of the (C1-C4) alkyl group include, for example, a straight chain such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group; an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. And the like. Of these, a methyl group, an ethyl group, and an n-propyl group are preferable, and a methyl group is more preferable.
Examples of the (C1-C4) alkoxy group include straight-chain or branched-chain groups, but straight-chain groups are preferred. Specific examples of the (C1-C4) alkoxy group include, for example, a straight chain such as a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group; an isopropoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. And branched chains such as groups. Of these, a methoxy group, an ethoxy group, and an n-propoxy group are preferable, and a methoxy group is more preferable.
Among the above, R ² is preferably a (C1-C4) alkyl group, and most preferably a methyl group.

In the above formula (2), R ³ represents a sulfo group or a carboxy group. Of these, a sulfo group is preferred.

  In the above formula (2), particularly preferred is a compound represented by the above formula (3). In this case, the effects of the present invention, ie, hue, sharpness, moisture resistance, water resistance, light resistance, and ozone gas resistance are particularly remarkable.

式（３）の化合物を含む反応液は、本発明の水性インク組成物の製造に直接使用することができる。しかし、反応液から単離し、乾燥、例えばスプレーを乾燥させ、次に水性インク組成物に加工することもできる。 The compound of the said Formula (3) is compoundable by the method of the said patent document 4. In addition, C.I. I. It is also possible to obtain it as Direct Orange 17 from the market.
As a specific synthesis example, for example, the following can be exemplified.
That is, an amine represented by the following formula (4) is diazotized by a conventional method, and a coupling reaction is performed with a coupler represented by the following formula (5) at room temperature (20 to 25 ° C.) with weak alkalinity (pH 8 to 9). Can be obtained. The aqueous ink composition of the present invention is suitable for the production of inks for writing and ink jet recording as a pigment that gives an orange color.

The reaction liquid containing the compound of the formula (3) can be directly used for the production of the aqueous ink composition of the present invention. However, it can also be isolated from the reaction liquid, dried, for example spray dried, and then processed into an aqueous ink composition.

  Examples of the salts of the compounds of the above formulas (1) to (3) include salts with alkali metals, alkaline earth metals, organic amine cations or ammonium ions. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include calcium and magnesium. Examples of the organic amine include methylamine, ethylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, and triisopropanolamine. Among these, preferred are alkali metals such as sodium, potassium and lithium, alkanolamine ions such as ammonium ion, monoethanolamine ion and diethanolamine ion. For example, in the case of a sodium salt, a sodium salt is obtained by adding sodium chloride to the reaction solution, salting out, and filtering. Further, a sodium salt is dissolved in water, and an acid is added to precipitate crystals in an acidic manner, followed by filtration. A free form dye is dissolved or suspended in water, and a base corresponding to the target salt, such as amines, A solution of each salt is obtained by adding and dissolving an alkali metal compound other than Na. From this solution, a salt other than the sodium salt can be obtained by precipitating, filtering, and drying each salt by a conventional method.

The aqueous orange ink composition of the present invention is obtained by dissolving component (I) and component (II) in water or an aqueous solvent (water containing a water-soluble organic solvent). When this aqueous ink composition is used as an ink for an ink jet printer, the compound used has a low content of inorganic substances such as metal cation chlorides and sulfates, for example, 1% by weight or less in the dye mixture. Is preferred. More specifically, it is preferable that the standard of the content is, for example, 1% by weight or less in the dye mixture as the total content of sodium chloride and sodium sulfate. More preferably, it is 0.5% by weight or less.
The content of the inorganic salt is, for example, Cl ⁻ and SO ₄ ²⁻ for ion chromatography, heavy metals for atomic absorption or ICP emission analysis, and Ca ²⁺ and Mg ²⁺ for ion chromatography, atomic absorption, It is measured by ICP emission spectrometry.
In order to obtain a dye having a lower inorganic content for the aqueous orange ink composition of the present invention, for example, a conventional method using a reverse osmosis membrane or the dye component of the present invention (the compound or dye mixture of the present invention) The dried product or wet cake, preferably a wet cake, is stirred in a solvent, for example, a mixed solvent of water-containing lower alcohol, preferably methanol and water, and then desalted by filtration and drying.
The aqueous orange ink composition of the present invention is obtained by dissolving the dye component in water or an aqueous solvent (water containing a water-soluble organic solvent described later). The pH of the ink is preferably about 6-11. When this aqueous orange ink composition is used in an ink jet recording printer, it is preferable to use a pigment component having a low content of inorganic salts such as metal cation chlorides and sulfates as described above.

  The aqueous ink composition of the present invention is prepared using water as a medium, and the pigment component is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, and still more preferably, in the aqueous ink composition. About 1 to 8% by weight is contained.

  The pigment component in the aqueous ink composition of the present invention can be obtained by mixing component (I) and component (II). The ratio of component (I) to component (II) is, for example, 99: 1 to 1:99, preferably 90:10 to 10:90, and more preferably 75:25 to 25:75, by weight.

  The water-based ink composition of the present invention may further contain a water-soluble organic solvent of about 60% by mass or less, preferably about 50% by mass or less, more preferably about 30% by mass or less, and the lower limit may be 0%. However, generally it is about 5 mass% or more, More preferably, it is 10 mass% or more, and 10-30 mass% is the most preferable.

  The aqueous orange ink composition of the present invention may contain an ink adjusting agent in an amount of about 0 to 10% by mass, preferably 5% by mass or less. The balance of the above components is water.

  Examples of the water-soluble organic solvent include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol, N, N-dimethylformamide or N, N -Carboxylic acid amides such as dimethylacetamide, lactams such as 2-pyrrolidone and N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one Cyclic ureas, acetone, methyl ethyl ketone, ketones such as 2-methyl-2-hydroxypentan-4-one or cyclic ethers such as keto alcohol, tetrahydrofuran, dioxane, ethylene glycol, 1,2- or 1,3-propylene Glycol, 1,2- or 1,4-butyle Monomers, oligomers or polyalkylenes having (C2-C6) alkylene units such as glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol Polyol (triol) such as glycol or thioglycol, glycerin, 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 tri (C1-C4) of polyhydric alcohols such as ethylene glycol monoethyl ether Alkyl ether, 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 ink preparation agents that can be used in the present invention include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust inhibitors, water-soluble UV absorbers, water-soluble polymer compounds, dye solubilizers, and surfactants. Etc.

  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 composition within the range of 8.0 to 11.0 without adversely affecting the ink composition to be prepared. . Examples of pH adjusters that can be used include alkanolamines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, lithium carbonate, and carbonate. Examples thereof include alkali metal carbonates such as sodium and potassium carbonate.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil 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 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, 82, 465, Olphine STG, etc. manufactured by Nissin Chemical Co., Ltd.).

The aqueous orange ink composition of the present invention can be produced by dissolving component (I) and component (II) in water or the above aqueous solvent (water-soluble organic solvent-containing water) together with the ink preparation agent and the like.
As component (I) and component (II), it is preferable to use a chromogen having a low content of metal cations such as chlorides and sulfates. About 1% by weight or less. In order to produce a pigment with a small amount of inorganic matter, a desalting treatment may be performed by a normal method such as a method using a reverse osmosis membrane.

  In the above production method, the order of dissolving the components is not particularly limited. The dye may be dissolved in water or the above-mentioned aqueous solvent (water-containing organic solvent-containing water) in advance, and the ink preparation agent may be added and dissolved, or after the dye is dissolved in water, the aqueous solvent and the ink preparation agent are added. It may be added and dissolved. The order may be different from this, and the aqueous ink composition of the present invention is produced by adding an aqueous solvent and an ink preparation agent to a reaction solution of a dye or a solution subjected to a desalting treatment with a reverse osmosis membrane. May be. In preparing the water-based ink composition of the present invention, the water used is preferably one having few impurities such as ion-exchanged water or distilled water. The aqueous ink composition of the present invention thus obtained may be subjected to microfiltration using a membrane filter or the like, if necessary, to remove impurities. In particular, when the aqueous ink composition of the present invention is used as an ink composition for an ink jet printer, it is preferable to perform microfiltration. The pore size of the filter used for microfiltration is usually 1 to 0.1 microns, preferably 0.8 to 0.2 microns.

  The water-soluble aqueous orange ink composition of the present invention is suitable for use in printing, copying, marking, writing, drawing, stamping, or recording methods, particularly in inkjet recording, but the most preferred use is for inkjet recording. In this case, a high quality orange print with good resistance to water, sunlight, ozone and friction is obtained. Further, the water-based ink composition of the present invention can be made to have an orange tone or a red tone as desired by blending an appropriate amount of a publicly known and used dye such as yellow or magenta.

The water-based orange ink composition of the present invention is preferably used for inkjet applications as an ink set composed of several colors of ink together with other color inks. The other colors are preferably provided with yellow, magenta, and cyan.
The yellow ink used is not particularly limited. I. Reactive Yellow 2, 3, 18, 81, 84, 85, 95, 99, 102, C.I. I. Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 72, 73, 79, 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219: 1, 220, 230, 232, 235, 241, 242, 246, C.I. I. An ink composition using Direct Yellow 8, 11, 12, 21, 28, 33, 39, 44, 49, 50, 85, 86, 87, 88, 89, 98, 100, 110, 144, 146, etc. as a dye. Can be mentioned.
The magenta ink to be used is not particularly limited. I. Reactive Red 3, 3: 1, 4, 13, 24, 29, 31, 33, 125, 151, 206, 218, 226, 245, C.I. I. Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97: 1, 106, 111, 114, 118, 119, 127, 131, 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415, C.I. I. Direct Red 2, 4, 6, 9, 17, 23, 26, 28, 31, 39, 54, 55, 57, 62, 63, 64, 65, 68, 72, 75, 76, 79, 80, 81, 83, 83: 1, 84, 89, 92, 95, 99, 111, 141, 173, 180, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, Examples thereof include ink compositions using 233, 240, 241, 242, 243, 247, etc. as dyes.
Examples of the cyan ink composition used include C.I. I. Reactive Blue 2, 5, 10, 13, 14, 15, 15: 1, 49, 63, 71, 72, 75, 162, 176, C.I. I. Acid Blue 1, 7, 9, 15, 23, 25, 40, 61: 1, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 127: 1, 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, 239, 249, 258, 260, 264, 277: 1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350, C.I. I. Direct Blue 1, 15, 22, 25, 41, 76, 77, 80, 86, 87, 90, 98, 106, 108, 120, 158, 163, 168, 199, 200, 201, 202, 226 etc. Ink compositions used as
In addition to these, an ink set including inks such as black, violet, green, and golden yellow may be used.

  The colored product of the present invention is colored with the above-described aqueous orange ink composition of the present invention. The material to be colored (recording material) 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 substrate. 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.

  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.), professional photo paper, super photo paper, matte photo paper , (All manufactured by Canon Inc.), PM photo paper, PM matte paper, Superfine glossy film (all manufactured by Epson Corp.), Premium Plus Photo Paper, Premium Glossy Film, Photo Paper (all by Nippon Hu -Let Packard Co., Ltd.) Photolike QP (Konica Co., Ltd.), etc., can be easily obtained from the market. Of course, it can also be used for plain paper.

  Among these ink-jet exclusive papers or glossy papers, it is known that images recorded on a recording material coated with a porous white inorganic substance on the surface are particularly prone to discoloration by ozone gas. Since the composition has excellent gas resistance, it exhibits particularly excellent effects when recording on such a recording material.

  In the above, as the porous white inorganic material used for coating, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, There are zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinc carbonate and the like.

  In order to record on the recording material by the ink jet recording method of the present invention, for example, a container filled with the aqueous ink composition of the present invention is set at a predetermined position of the ink jet printer and recorded on the recording material by a normal method. Can be done. In the inkjet recording method of the present invention, a green ink composition, a blue (or violet) ink composition, and a water-based ink composition of the present invention, in addition to a publicly known yellow ink composition, magenta ink composition, and cyan ink composition. (Orange) is used in combination with a black ink composition or the like as necessary. The ink composition of each color is filled in each container, and these containers are used by being set (loaded) in a predetermined position of the ink jet printer in the same manner as the container filled with the aqueous ink composition 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 water-based orange ink composition of the present invention gives a clear orange color to a printed image, and exhibits a high clear hue particularly on inkjet glossy paper. Further, when used together with other yellow and magenta inks, it is possible to produce a color tone that cannot be produced by mixing the normal yellow ink and magenta ink, and a recorded matter with excellent color expression can be obtained.

The aqueous orange ink composition according to the present invention does not precipitate or separate during storage. In addition, when the aqueous ink composition of the present invention is used in ink jet recording, the ejector (ink head) is not clogged, and the ink jet printer is under recirculation for a relatively long time by the continuous ink jet printer or on demand type ink jet printer. Even in intermittent use, the physical properties do not change.
The aqueous orange ink composition of the present invention has a hue and sharpness suitable for ink jet recording. Accordingly, a photographic image can be recorded more accurately.
Furthermore, the water-based orange ink composition of the present invention gives an orange image excellent in various fastnesses such as moisture resistance, water resistance, light resistance and ozone gas resistance, in particular, light resistance and ozone gas resistance. Therefore, the color fading phenomenon of the ink jet recorded image can be suppressed.

EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. Unless otherwise specified, “part” and “%” in the text are based on mass, and the reaction temperature is the internal temperature.
Among the synthesized compounds, those measured for λmax (maximum absorption wavelength) showed measured values in an aqueous solution at pH 7. Moreover, in each structural formula of the compound obtained in the Example, acidic functional groups, such as a carboxy group and a sulfo group, were described in the form of a free acid. The solubility of the compounds of the present invention obtained in Synthesis Examples in water at room temperature was 100 g / L or more.

得られた反応液に、水２８０部を追加し、液温を８５〜８８℃に調整しグルコース１２部を加えたて２時間攪拌し、還元反応を完結させた。次いで、塩酸を用いてｐＨを９．０〜９．５に調整し、塩化ナトリウムを用いて塩析を行い、濾過した。得られたケーキ全量を水２０００部に溶解し、メタノール２０００部の添加により晶析させ、結晶を濾過、分離することにより脱塩した。次いで得られた結晶を乾燥して、上記式（１）で表される化合物１９２部を得た（λｍａｘ：４１３ｎｍ）。 [Synthesis Example 1]
In 675 parts of water, 115 parts of the compound of the following formula (6), 98 parts of the compound of formula (7), 61 parts of a 48% aqueous sodium hydroxide solution and 11 parts of ethylene glycol were added and stirred at 98 ° C. for 10 hours to conduct a condensation reaction. Was completed.

280 parts of water was added to the obtained reaction liquid, the liquid temperature was adjusted to 85 to 88 ° C., 12 parts of glucose was added, and the mixture was stirred for 2 hours to complete the reduction reaction. Next, the pH was adjusted to 9.0 to 9.5 using hydrochloric acid, salted out using sodium chloride, and filtered. The total amount of the cake obtained was dissolved in 2000 parts of water and crystallized by adding 2000 parts of methanol, and the crystals were desalted by filtration and separation. Subsequently, the obtained crystal was dried to obtain 192 parts of a compound represented by the above formula (1) (λmax: 413 nm).

[Synthesis Example 2]
By a conventional method, 32.0 parts of dehydrothio-p-toluidinesulfonic acid (compound represented by the above formula (4)) is diazotized with hydrochloric acid and sodium nitrite at room temperature (20 to 25 ° C.). Do. After dissolving 28.4 parts of 1-p-sulfophenyl-5-pyrazolone-3-carboxylic acid (compound represented by the above formula (5)) with caustic soda at pH 8-9, the above-mentioned dehydrothio-p-toluidine sulfone By performing a coupling reaction with an acid diazonium salt at 20 to 25 ° C. and pH 8 to 9, 52.0 parts of the compound represented by the above formula (3) was obtained (λmax: 453 nm).

[Example 1]
[(A) Ink adjustment]
The composition liquid shown in Table 1 is prepared using the compound of Formula (1) obtained in Synthesis Example 1 and Formula (3) obtained in Synthesis Example 2, and filtered through a 0.45 μm membrane filter. Thus, an aqueous ink composition of the present invention was obtained. In addition, ion-exchange water was used for water. Further, water and aqueous ammonia were added so that the pH of the water-based ink composition was 8-9 and the total amount was 100 parts.

[(B) Inkjet recording by inkjet printer]
Inkjet recording was performed on two types of glossy paper A (made of PT-101 Canon) and glossy paper B (made of Chris Pier Epson) having a dye receiving layer using an ink jet printer (made by ip4500 Canon).

実施例１と同様にインクジェットプリンターによるインクジェット記録を行った。 [Comparative Example 1]
Using the compound of formula (1) used in Example 1, the ink composition shown in Table 2 was prepared, and filtered through a 0.45 μm membrane filter to obtain the aqueous ink composition of the present invention. In addition, ion-exchange water was used for water. Further, water and aqueous ammonia were added so that the pH of the water-based ink composition was 8-9 and the total amount was 100 parts.

Inkjet recording by an inkjet printer was performed in the same manner as in Example 1.

実施例１と同様にインクジェットプリンターによるインクジェット記録を行った。 [Comparative Example 2]
Using the compound of the formula (3) used in Example 2, the ink composition shown in Table 3 was prepared and filtered through a 0.45 μm membrane filter to obtain the aqueous ink composition of the present invention. In addition, ion-exchange water was used for water. Further, water and aqueous ammonia were added so that the pH of the water-based ink composition was 8-9 and the total amount was 100 parts.

Inkjet recording by an inkjet printer was performed in the same manner as in Example 1.

オレンジの鮮明性Ｃ＊を評価する際には、Ｌ＊、ａ＊、ｂ＊のいずれかを基準とする必要があるため、各記録紙のＬ＊が一致するところで以下の評価をおこなった。表４より、実施例１は、明度Ｌ＊を一致させたときに、比較例１、２よりもＣ＊値が高く鮮明性が高い色相であることがわかる。
[２．キセノン耐光性試験]
光沢紙にプリントした試験片を、キセノンウェーザーメーターを用い、１００ｋＬｕｘで１６８時間照射し、試験前後のＤｙを測定し照射後の残存率を算出した。
[３．耐オゾンガス性試験]
光沢紙にプリントした試験片を、オゾンウェザーメーターを用いてオゾン濃度１０ｐｐｍ、湿度６０％ＲＨ、温度２４℃の環境下に２４時間放置し、試験前後の色差（△Ｅ）を測定した。
実施例１、比較例１、比較例２の耐光性、耐オゾン性の結果を表５に示す。

表５より、比較例２は、耐オゾン性は良好なものの耐光性はかなり劣る。一方、比較例１は、耐光性は良好なものの耐オゾン性は劣る。しかし、比較例１に用いた式（１）の化合物と比較例２に用いた式（３）の化合物を配合した実施例１は耐光性、耐オゾン性とも良好である。 [(C) Evaluation of recorded image]
[1. Hue evaluation]
[1-1. Hue evaluation on glossy paper]
Hue and sharpness of recorded image: The recording paper was color-measured using a colorimetric system (GRETAG SPM50: manufactured by GRETAG), and L *, a *, and b * values were calculated. The sharpness is evaluated by calculating C * = ((a *) ² + (b *) ² ) ^1/2 from the chromaticity (a *, b *) when the lightness L * values of each recording paper are combined. did. Colorimetry was performed with light source D65 and condition DIN NB.
Table 4 shows the hue results of Example 1, Comparative Example 1, and Comparative Example 2.

When evaluating the clarity C * of orange, it is necessary to use any of L *, a *, and b * as a reference. Therefore, the following evaluation was performed when L * of the respective recording papers coincided. From Table 4, it can be seen that Example 1 is a hue having a higher C * value and higher clarity than Comparative Examples 1 and 2 when the lightness L * is matched.
[2. Xenon Light Resistance Test]
The test piece printed on glossy paper was irradiated with a xenon weather meter at 100 kLux for 168 hours, Dy before and after the test was measured, and the residual ratio after irradiation was calculated.
[3. Ozone gas resistance test]
The test piece printed on glossy paper was left in an environment of ozone concentration 10 ppm, humidity 60% RH, temperature 24 ° C. for 24 hours using an ozone weather meter, and the color difference (ΔE) before and after the test was measured.
Table 5 shows the results of light resistance and ozone resistance of Example 1, Comparative Example 1, and Comparative Example 2.

From Table 5, Comparative Example 2 has good ozone resistance, but is inferior in light resistance. On the other hand, Comparative Example 1 has good light resistance but poor ozone resistance. However, Example 1 in which the compound of Formula (1) used in Comparative Example 1 and the compound of Formula (3) used in Comparative Example 2 were blended has good light resistance and ozone resistance.

From the above results, it was confirmed that the water-based orange ink composition of the present invention has a hue and sharpness suitable for ink jet recording, and is excellent in fastness (ozone gas resistance and light resistance).
Therefore, the dye composition of the present invention is also used in the ink jet recording method in which recording is performed on a recording material using each of four or more aqueous ink compositions containing yellow, magenta, cyan and orange. The object gives a recorded image excellent in sharpness and fastness, and is very useful in inkjet applications.

Claims (10)

A compound represented by the following formula (1) as a component (I) or a salt thereof, and an aqueous orange containing a dye having a λmax (maximum absorption wavelength) measured in an aqueous solution of pH 7 as a component (II) of 420 nm or more and 500 nm or less Ink composition.

The aqueous orange ink composition according to claim 1, wherein the component (II) is a compound represented by the following formula (2) or a salt thereof.

(In formula (2), ^{R 1} represents a sulfo group or carboxy group, ^{R 2} represents a (C1-C4) alkyl or (C1-C4) alkoxy group, ^{R 3} represents a sulfo group or a carboxy group. ) ^3. The aqueous orange ink composition according to claim 2, wherein, in the formula (2), R ¹ and R ³ are a sulfo group, and R ² is a methyl group. The aqueous orange ink composition according to any one of claims 1 to 3, wherein the component (II) is a compound represented by the following formula (3) or a salt thereof.

The aqueous orange ink composition according to any one of claims 1 to 4, which is for inkjet recording. An ink set comprising the aqueous orange ink composition according to any one of claims 1 to 5. The ink set according to claim 6, comprising at least four colors of yellow, magenta, cyan, and orange containing the aqueous orange ink composition according to claim 1. An ink jet recording method using the ink set according to claim 6. The inkjet recording method according to claim 8, wherein the recording material is an information transmission sheet. A colored body colored with the aqueous orange ink composition according to claim 1.