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WO2012090933A1 - Composé azoïque soluble dans l'eau ou sel de celui-ci, composition d'encre, et objet coloré - Google Patents

Composé azoïque soluble dans l'eau ou sel de celui-ci, composition d'encre, et objet coloré Download PDF

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Publication number
WO2012090933A1
WO2012090933A1 PCT/JP2011/080063 JP2011080063W WO2012090933A1 WO 2012090933 A1 WO2012090933 A1 WO 2012090933A1 JP 2011080063 W JP2011080063 W JP 2011080063W WO 2012090933 A1 WO2012090933 A1 WO 2012090933A1
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WIPO (PCT)
Prior art keywords
water
ink
salt
ink composition
compound
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PCT/JP2011/080063
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English (en)
Japanese (ja)
Inventor
陵太郎 森田
祐樹 澁谷
由桂 宍倉
梶浦　典子
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日本化薬株式会社
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Priority to JP2012550935A priority Critical patent/JPWO2012090933A1/ja
Publication of WO2012090933A1 publication Critical patent/WO2012090933A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/02—Disazo dyes
    • C09B33/08—Disazo dyes in which the coupling component is a hydroxy-amino compound
    • C09B33/10—Disazo dyes in which the coupling component is a hydroxy-amino compound in which the coupling component is an amino naphthol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes

Definitions

  • the present invention relates to a water-soluble disazo compound or a salt thereof, an ink composition containing the same, and a colored body colored with these.
  • ink ejection methods have been developed as recording methods using an ink jet printer, which is one of the representative methods. These all generate ink droplets and attach them to various recording materials (paper, film, fabric, etc.) for recording. In this method, since the recording head and the recording material are not in direct contact with each other, no noise is generated and the method is quiet. In addition, since it has the characteristics that it is easy to downsize, speed up, and colorize, it has been rapidly spreading in recent years and is expected to grow greatly in the future. Conventionally, inks such as fountain pens and felt pens, and inks for ink-jet recording have been used in which water-soluble pigments (dyes) are dissolved in an aqueous medium.
  • inks such as fountain pens and felt pens, and inks for ink-jet recording have been used in which water-soluble pigments (dyes) are dissolved in an aqueous medium.
  • a water-soluble organic solvent is added to these water-based inks in order to prevent clogging of ink at a pen tip or an ink discharge nozzle.
  • These inks give a recorded image of sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, have little bleeding, and have excellent storage stability. Such performance is required.
  • Ink jet nozzle clogging occurs when the water in the ink evaporates in the vicinity of the nozzle before other solvents and additives, and the pigment solidifies and precipitates when the composition state is low in water and high in solvents and additives.
  • the very important required performances is that solids are not easily deposited even when the moisture content in the ink is low. For this reason, high solubility in solvents and additives is one of the properties required for pigments.
  • a method for eliminating nozzle clogging a method using a dye having a high printing density is known. By using a pigment having a high printing density, the pigment content in the ink can be reduced while maintaining the conventional printing density. This not only makes it difficult to precipitate the dye, but is also advantageous in terms of cost, and development of a dye having a high printing density is desired.
  • the color area that can be expressed in a single color or mixed color becomes narrow, and the range of the color area that is desired to be expressed may be insufficient. For this reason, development of highly saturated pigments and inks containing them is desired.
  • the ink performance is required to be stable for long-term storage, high in recorded image density, and excellent in fastness such as water resistance, moisture resistance, light resistance and gas resistance. It is done.
  • the gas resistance means that a gas having an oxidizing action (also referred to as an oxidizing gas) existing in the air reacts with a dye (dye) of a recorded image on the recording material or in the recording material to record.
  • ozone gas is considered to be a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Since this discoloration phenomenon is characteristic of ink jet recorded images, improvement of ozone gas resistance is an important technical problem in this field.
  • inkjet printers Due to recent developments in inkjet technology, the speed of inkjet recording (printing) has been dramatically improved. For this reason, similar to laser printers using electronic toner, there is a market trend to use inkjet printers for printing documents on plain paper, which is the main application in office environments. Inkjet printers have the advantage that the type of recording paper is not limited, and the price of the printer itself is low, and the spread is particularly widespread in small to medium-sized office environments such as small offices and home offices (SOHO). As described above, when an inkjet printer is used for printing on plain paper, hue, color (printing) density, and water resistance tend to be more important among the qualities required for printed matter. In order to satisfy these performances, a method using a pigment ink has been proposed.
  • pigment ink does not dissolve in water-based ink, it does not enter a solution state, but is a dispersed ink. Therefore, when this is used for ink jet recording, there are problems with the stability of the ink itself and the nozzles of the recording head. Problems such as clogging occur.
  • pigment ink when pigment ink is used, there is often a problem in abrasion resistance. In the case of a dye ink, such a problem is considered to be relatively difficult to occur.
  • the water resistance is extremely inferior to that of a pigment ink, and an improvement to the problem is strongly desired.
  • dye ink tends to cause a problem that a dye attached to the surface of plain paper by ink jet recording penetrates more quickly toward the back side of the paper, resulting in a decrease in color density.
  • the ink receiving layer As one method for obtaining a photographic image-recorded inkjet image, there is a method of providing an ink receiving layer on the surface of a recording material.
  • the ink receiving layer provided for such a purpose often contains a porous white inorganic substance in order to speed up drying of the ink and to reduce bleeding of the pigment with high image quality.
  • the above-described discoloration due to ozone gas is noticeable.
  • With the recent spread of digital cameras and color printers there are increasing opportunities to print images obtained with digital cameras and the like as photographic image quality at home, so the above-mentioned color change of recorded images due to oxidizing gas is regarded as a problem. .
  • yellow dyes Compared to the other three primary colors, magenta and cyan, yellow dyes have been proposed that have good resistance to oxidizing gas as well as light resistance. However, yellow dyes and yellow inks for inkjet recording that sufficiently satisfy the high sharpness and various fastnesses required by the market have not been obtained yet.
  • Patent Document 1 discloses a yellow anionic azo compound having light resistance and water fastness.
  • Patent Document 2 discloses a yellow water-soluble azo compound that is highly soluble in water and has moisture resistance, ozone gas resistance, and light resistance.
  • Patent Document 3 discloses a yellow water-soluble azo compound that is highly soluble in water, has moisture resistance, ozone gas resistance, and light resistance, and is particularly excellent in fastness such as water resistance on plain paper.
  • Patent Document 4 discloses a water-soluble yellow pigment having high solubility in water or a water-soluble organic solvent, high image printing density, and excellent image light resistance and ozone gas resistance.
  • the present invention is a water-soluble yellow dye (compound) having high solubility in water, high color developability (printing density) of recorded images, and excellent chroma, and various recordings containing the same, particularly inkjet recording.
  • An object of the present invention is to provide a yellow ink composition.
  • the present invention 1) A water-soluble azo compound represented by the following formula (1) or a salt thereof, (In the formula, x represents an integer of 2 to 4, and the group A represents an amino group represented by any of the following formulas (2) to (6).) (In formula (2), w represents an integer of 2 to 6.) (In formula (3), v represents an integer of 0 to 3.)
  • x is 3, the water-soluble azo compound or salt thereof according to 1) above, 3) The water-soluble azo compound represented by the above formula (1) or the salt thereof according to the above 1) represented by the following formula (7): 4) An ink composition containing the water-soluble azo compound or salt thereof according to any one of 1) to 3) above; 5) The ink composition as described in 4) above, further comprising a water-soluble organic solvent, 6) The ink composition according to 4) or 5), which is for inkjet recording; 7) An ink jet recording method in which the ink composition according to any one of 4) to 6) above is used as an ink, and ink droplets of the ink are ejected in accordance with a recording signal to adhere to a recording material, and recording is performed; 8) The inkjet recording method according to 7), wherein the recording material is an information transmission sheet; 9) The inkjet recording method according to 8), wherein the information transmission sheet is a plain paper or a sheet having an ink receiving layer
  • the water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof has a high solubility in water, and for example, in the process of producing the ink composition of the present invention containing the compound or a salt thereof, It has the characteristic that the filterability with respect to a membrane filter is favorable.
  • an image recorded by the ink composition of the present invention containing the compound of the present invention is excellent in print density and saturation as compared with the image using the conventional compound.
  • the water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof, and an ink composition containing the water-soluble azo compound are extremely suitable for various recording ink applications, particularly for ink jet recording ink applications. Useful.
  • the present invention will be described in detail.
  • the water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof is a water-soluble yellow dye.
  • acidic functional groups such as sulfo groups and carboxy groups are represented in the form of free acids.
  • the present invention includes both the water-soluble azo compound represented by the above formula (1) or a salt of the compound, and both are always described as “compound or salt thereof”. It is complicated.
  • the term “the (water-soluble azo) compound of the present invention or a salt thereof” including both “the present invention (water-soluble azo) compound” will be simply described as “the (water-soluble azo) compound of the present invention”.
  • the compound of the present invention is represented by the above formula (1).
  • x represents an integer of 2 to 4, preferably 3.
  • the group A represents an amino group represented by any one of the above formulas (2) to (6).
  • w in the above formula (2) represents an integer of 2 to 6, preferably 2.
  • v represents an integer of 0 to 3, preferably 0.
  • the group A is preferably an amino group represented by the above formula (2) or (6), and more preferably an amino group represented by the above formula (6).
  • a more preferred compound of the above formula (1) is a compound represented by the above formula (7).
  • the compound of the present invention represented by the above formula (1) can be produced, for example, as follows.
  • the groups A, v, w, and x that are appropriately used in the following formulas (AA) to (J) represent the same meaning as in the above formula (1).
  • a compound represented by the following formula (AA) obtained from commercially available 2-aminophenol as a raw material is converted into a methyl- ⁇ -sulfonic acid derivative represented by the following formula (B) using sodium bisulfite and formalin. To do. Then, by a conventional method, 5-amino-2-chlorobenzoic acid represented by the following formula (C) is diazotized, and the methyl- ⁇ -sulfonic acid derivative represented by the following formula (B) obtained above is A coupling reaction is carried out at a reaction temperature of 0 to 15 ° C. and a pH of 2 to 4, followed by a hydrolysis reaction at a reaction temperature of 80 to 95 ° C. and a pH of 10.5 to 11.5. Is obtained. This synthesis is a method according to the method described in JP-A-2006-152264.
  • Specific examples of the amine represented by the formula (F) include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, and 6-aminohexanol.
  • Specific examples of the amine represented by the above formula (G) include methylamine, ethylamine, n-propylamine, n-butylamine and the like.
  • the amine represented by the above formula (H) can be easily obtained as a commercial product as t-butylamine
  • the amine represented by the above formula (I) can be easily obtained as a 2-furfurylamine.
  • the amine represented by the above formula (J) can be easily obtained as a commercial product as iminodiacetic acid.
  • the compound represented by the above formula (1) exists also as a free acid or a salt thereof.
  • the salt of the compound represented by the formula (1) include salts with inorganic or organic cations.
  • the inorganic cation salt include alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts (NH 4 + ) and the like.
  • the organic cation salt include, but are not limited to, a quaternary ammonium salt represented by the following formula (8).
  • Z 1 ⁇ Z 4 represent each independently a hydrogen atom, a C1-C4 alkyl group, hydroxy C1-C4 alkyl group, or a hydroxy C1-C4 alkoxy C1-C4 alkyl group, Z 1 At least one of ⁇ Z 4 is a group other than a hydrogen atom.
  • examples of the C1-C4 alkyl group in Z 1 to Z 4 include methyl, ethyl and the like.
  • examples of the hydroxy C1-C4 alkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like.
  • examples of the hydroxy C1-C4 alkoxy C1-C4 alkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) butyl, 2- (hydroxyethoxy ) Butyl and the like.
  • alkali metal salts such as sodium, potassium and lithium salts
  • organic quaternary ammonium such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine salts. Salt; ammonium salt; and the like.
  • lithium salts, sodium salts, and ammonium salts are more preferable.
  • the salt or free acid of the compound represented by the above formula (1) can be easily obtained by the following method or the like.
  • the reaction solution after completion of the final step, or an aqueous solution containing a salt of the compound represented by the above formula (1) for example, acetone or C1-C4
  • a method of adding a water-soluble organic solvent such as alcohol; a method of salting out by adding sodium chloride; and the like It can be obtained as a wet cake.
  • an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is separated by filtration, whereby the compound represented by the above formula (1) Or a mixture of a free acid and a sodium salt in which a part of the compound represented by the formula (1) is a sodium salt.
  • an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added to adjust the pH appropriately to, for example, pH 1 to 3, An ammonium salt of the compound represented by the above formula (1) can be obtained by separating the precipitated solid by filtration.
  • a mixture of an ammonium salt of the compound represented by the above formula (1) and a sodium salt of the compound represented by the above formula (1) by appropriately adjusting the amount or / and pH of ammonium chloride to be added; It is also possible to obtain a mixture of the free acid and ammonium salt of the compound represented by (1); Further, as described later, a free acid solid can be directly obtained by adding a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) to the reaction solution after completion of the above reaction. In this case, the wet cake of the free acid of the compound represented by the above formula (1) is added to water and stirred, for example, potassium hydroxide; lithium hydroxide; ammonia water; represented by the above formula (8).
  • a mineral acid for example, hydrochloric acid, sulfuric acid, etc.
  • a salt of organic quaternary ammonium hydroxide, etc. potassium salt, lithium salt, ammonium salt, quaternary ammonium salt, etc. according to each added compound can be obtained.
  • a mixed salt of lithium salt and sodium salt, etc . and a mixture of lithium salt, sodium salt, and ammonium salt Salts and the like can also be prepared.
  • the salt of the compound represented by the above formula (1) may change the physical properties such as solubility or the ink performance when used as an ink depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the intended ink performance.
  • the compound of the present invention represented by the above formula (1) can be isolated as a solid free acid by adding a mineral acid such as hydrochloric acid, and the resulting free acid solid can be isolated with water or, for example, By washing with acidic water such as hydrochloric acid water, inorganic salts (inorganic impurities) contained as impurities, such as sodium chloride and sodium sulfate, can be removed.
  • acidic water such as hydrochloric acid water
  • inorganic salts inorganic impurities contained as impurities, such as sodium chloride and sodium sulfate
  • Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; ammonium hydroxide (ammonia water); Etc.
  • Examples of the organic base include, for example, organic amines corresponding to the quaternary ammonium represented by the above formula (8), for example, alkanolamines such as diethanolamine and triethanolamine, but are not limited thereto. .
  • the compound of the present invention is suitable for dyeing natural and synthetic fiber materials or blended products, and also for producing inks for writing and ink jet recording.
  • the reaction solution after completion of the final step in the synthesis reaction of the compound of the present invention represented by the above formula (1) can be directly used for the production of the ink composition of the present invention.
  • the reaction solution or the like is dried by the above-described method or a spray drying method to isolate the compound, the obtained compound can be processed into an ink composition.
  • the compound represented by the above formula (1) is mixed with water or a mixed solution (also referred to as an aqueous medium) of water and a water-soluble organic solvent (an organic solvent that can be mixed with water). It is dissolved and an ink preparation agent is added if necessary.
  • a metal cation chloride contained as an impurity such as sodium chloride
  • sulfate such as sodium sulfate
  • Is preferred when this ink composition is used as an ink for an ink jet printer, a metal cation chloride contained as an impurity, such as sodium chloride; sulfate, such as sodium sulfate; Is preferred.
  • the total content of sodium chloride and sodium sulfate is about 1% by mass or less with respect to the total mass of the compound represented by the above formula (1), and the lower limit is 0% by mass, that is, the detection device. Or below the detection limit.
  • a method for producing a compound having a small amount of inorganic impurities for example, a method using a known reverse osmosis membrane; or a dried product or wet cake of the compound of the present invention, for example, acetone or C1-C4 alcohol (for example, methanol, ethanol,
  • acetone or C1-C4 alcohol for example, methanol, ethanol
  • water-soluble organic solvents such as isopropanol or the like, or water-containing water-soluble organic solvents, suspension purification or crystallization methods, and the like can be mentioned. Desalination treatment and the like may be performed by these methods.
  • the compound represented by the formula (1) is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 2% by mass in the total mass of the ink composition. 8% by mass is contained.
  • the ink composition of the present invention is prepared using water as a medium, and may optionally contain a water-soluble organic solvent and an ink preparation agent as long as the effects of the present invention are not impaired.
  • the water-soluble organic solvent dissolves the dye; prevents the composition from drying (maintains a wet state); adjusts the viscosity of the composition; promotes penetration of the dye into the recording material; adjusts the surface tension of the composition;
  • the ink composition of the present invention is preferably contained.
  • ink preparation agent examples include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, ultraviolet absorbers, viscosity adjusting agents, dye dissolving agents, antifading agents, surface tension adjusting agents, antifoaming agents, etc.
  • Known additives may be mentioned.
  • the content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass, preferably 0%, based on the total mass of the ink composition of the present invention. It is preferable to use up to 15% by mass.
  • the balance other than the compound represented by the above formula (1), the water-soluble organic solvent, and the ink preparation agent is water.
  • water-soluble organic solvent examples include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; N, N-dimethylformamide, N, N Amides such as dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyrimido-2 Heterocyclic ketones such as -one; ketones or keto alcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1, 2- or 1, 3-propylene glycol, 1,2- or Mono, oligo having C
  • the water-soluble organic solvent includes substances that are solid at room temperature, such as trimethylolpropane. Even if the substance is solid, it shows water solubility, and an aqueous solution containing the substance shows the same properties as the water-soluble organic solvent and can be used with the expectation of the same effect. Therefore, in this specification, for the sake of convenience, such a solid substance is included in the category of a water-soluble organic solvent as long as it can be used in expectation of the same effect as described above.
  • water-soluble organic solvent Preferred as the above water-soluble organic solvent are isopropanol, glycerin, mono, di, or triethylene glycol, dipropylene glycol, 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, trimethylolpropane.
  • butyl carbitol more preferably isopropanol, glycerin, diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and butyl carbitol.
  • antiseptic / antifungal agents examples include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts.
  • Examples of the organic halogen compound include sodium pentachlorophenol
  • examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide
  • examples of the isothiazoline compound include 1,2-benz Isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-3- Onmagnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like can be mentioned.
  • antiseptic / antifungal agents include sodium acetate, sodium sorbate, sodium benzoate, etc .; and trade names Proxel RTM GXL (S) and Proxel RTM XL-2 (S) manufactured by Arch Chemical Co., etc. Is mentioned. In the present specification, the superscript “RTM” means a registered trademark.
  • any substance can be used as long as it can control the pH of the ink in the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink.
  • alkanolamines such as diethanolamine and triethanolamine
  • hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • ammonium hydroxides carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate Salts
  • aminosulfonic acids such as taurine; and the like.
  • chelating reagent examples include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like.
  • rust preventive agent examples include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
  • the ultraviolet absorber examples include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds.
  • a compound that absorbs ultraviolet rays and emits fluorescence such as a so-called fluorescent whitening agent, represented by a benzoxazole-based compound, can be used.
  • examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, and examples thereof include polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.
  • dye solubilizer examples include urea, ⁇ -caprolactam, ethylene carbonate, and the like. Of these, urea is preferably used.
  • the anti-fading agent is used for the purpose of improving image storage stability.
  • various organic and metal complex antifading agents can be used.
  • organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Includes nickel complexes and zinc complexes.
  • Examples of the surface tension adjusting agent include surfactants, and examples include anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants.
  • anionic surfactants include alkyl sulfocarboxylates, ⁇ -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, alkylaryl sulfonate, diethylsulfosuccinate Salts, diethylhexylsulfosuccinate, dioctylsulfosuccinate and the like.
  • Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
  • Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, etc. Is mentioned.
  • Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl -1-hexyne-3-acetylene glycol (alcohol) -based ol; Nissin Chemical Industry Co., Ltd. trade name Surfynol
  • antifoaming agents include highly oxidized oils, glycerin fatty acid esters, fluorines, and silicone compounds.
  • the surface tension of the ink composition of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m, and the viscosity is preferably 30 mPa ⁇ s or less, more preferably 20 mPa ⁇ s or less. .
  • the ink composition of the present invention there is no particular limitation on the order of dissolving each agent such as an additive.
  • the water used for preparing the ink composition is preferably water with few impurities such as ion exchange water and distilled water.
  • microfiltration may be performed using a membrane filter or the like to remove impurities in the ink composition.
  • the pore size of the filter used for microfiltration is usually 1 to 0.1 ⁇ m, preferably 0.8 to 0.1 ⁇ m.
  • the ink composition containing the compound of the present invention is suitable for use in printing, copying, marking, writing, drafting, stamping, or recording (printing), particularly inkjet recording.
  • the ink composition of the present invention is less likely to precipitate solids even when dried in the vicinity of the nozzles of the recording head of an ink jet printer, and for this reason, the recording head is also less likely to block.
  • the ink jet recording method of the present invention As a method for recording on a recording material by the ink jet recording method of the present invention, the following method may be mentioned. That is, a container filled with the ink composition of the present invention is loaded into a predetermined position of an ink jet printer, the ink composition of the present invention is used as ink, and ink droplets of the ink are ejected according to a recording signal to be recorded. This is a method for recording on a material.
  • Some inkjet printers use, for example, a piezo method using mechanical vibration; a bubble jet (registered trademark) method using bubbles generated by heating; and the like.
  • the ink jet recording method of the present invention can be used by any method.
  • ink composition of the present invention can also be used as such an ink set. Further, the ink composition of the present invention may be used for one of the ink sets, and a known ink (composition) may be used for the other.
  • the ink composition of the present invention may be a yellow ink composition containing the compound of the present invention and a known yellow dye for the purpose of fine-tuning the hue within a range that does not impair the effects obtained by the present invention.
  • the compound of the present invention can be used in combination with a magenta dye or a cyan dye for the purpose of toning inks of other colors, such as black ink, or for preparing red ink or green ink.
  • the ink composition of the present invention can be used in combination with inks of various colors such as magenta, cyan, and, if necessary, green, blue (or violet), red, and black.
  • each color ink may be filled in each container, and these containers may be loaded into a predetermined position of the ink jet printer and used for ink jet recording.
  • Examples of the recording material used in the inkjet recording method of the present invention include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like.
  • a transmission sheet is preferred.
  • the information transmission sheet is not particularly limited, and a plain paper as well as a surface-treated sheet, specifically, a paper, synthetic paper, a substrate such as a film provided with an ink receiving layer, or the like is used.
  • the ink receiving layer is a layer having an action such as absorbing ink and accelerating its drying.
  • the ink receiving layer is formed by, for example, a method of impregnating or coating the base material with a cationic polymer; inorganic fine particles capable of absorbing the pigment in the ink together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone on the surface of the base material. It is provided by the method of coating; Examples of the material of the inorganic fine particles that can absorb the coloring matter in the ink include porous silica, alumina sol, and special ceramics.
  • the information transmission sheet having such an ink receiving layer is usually called an inkjet exclusive paper, an inkjet exclusive film, a glossy paper, a glossy film or the like.
  • Typical examples of commercially available information transmission sheets having an ink receiving layer are Canon Inc., trade name Professional Photo Paper, Canon Photographic Paper / Glossy Pro [Platinum Grade], and Glossy Gold; Seiko Epson ( Co., Ltd., trade name photo paper Crispia (high gloss), photo paper (gloss); Nihon Hewlett-Packard Co., Ltd., trade name Advanced Photo Paper (gloss); Fuji Film Co., Ltd. Pro; manufactured by Brother Industries, Ltd., trade name: photographic glossy paper BP71G; Further, plain paper means paper that is not particularly provided with an ink receiving layer, and many different types are commercially available depending on the application.
  • plain paper for inkjet recording, double-sided fine plain paper (manufactured by Seiko Epson Corporation); PB PAPER GF-500 (manufactured by Canon Inc.); Multipurpose Paper, All-in-one Printing Paper ( Hewlett Packard); and the like.
  • plain paper copy (PPC) paper or the like whose use is not limited to ink jet recording is also plain paper.
  • the colored product of the present invention comprises (a) the water-soluble azo compound of the present invention; (b) the ink composition of the present invention containing the compound; and (c) the invention containing the compound and a water-soluble organic solvent.
  • the substance to be colored is not particularly limited, and examples thereof include, but are not limited to, the recording material described above.
  • the above-mentioned recording material is colored.
  • a coloring method for the substance is not particularly limited, and examples thereof include a printing method such as a dip dyeing method, a textile printing method, and screen printing, an ink jet recording method of the present invention, and the ink jet recording method of the present invention is preferable.
  • a colored body colored by the ink jet recording method of the present invention is preferable.
  • the water-soluble azo compound of the present invention represented by the above formula (1) is excellent in solubility in water or a water-soluble organic solvent. Moreover, it has the characteristic that the filterability with respect to a membrane filter, for example in the process of manufacturing the ink composition of this invention is favorable.
  • the ink composition of the present invention is very clear on a recording material such as plain paper and an information transmission sheet having an ink receiving layer, has a high saturation and printing density, and is capable of producing a yellow recorded image of an ideal hue. give. Therefore, it is also possible to faithfully reproduce a photographic color image on paper.
  • the ink composition of the present invention has very good storage stability without solid precipitation, physical property change, hue change, etc. after long-term storage.
  • the ink composition of the present invention uses a continuous ink jet printer, and is used physically even when the ink is recirculated at a relatively long time interval or intermittently used by an on-demand ink jet printer. No change in properties.
  • the image recorded on the information transmission sheet having the ink receiving layer by the ink composition of the present invention has various fastness properties such as water resistance, moisture resistance, ozone gas resistance, abrasion resistance, and light resistance,
  • the ozone gas property is good, and for this reason, the long-term storage stability of photographic images is also excellent.
  • it is also excellent in color development properties such as saturation, brightness, and print density on plain paper, and in particular, high saturation.
  • the water-soluble azo compound of the present invention represented by the above formula (1) and the ink composition of the present invention containing the same are extremely useful for various recording ink applications, particularly for ink jet recording. It is.
  • Example 1 (Process 1) 17.2 parts of 5-amino-2-chlorobenzoic acid was dissolved in 200 parts of water while adjusting the pH to 6 with sodium hydroxide, and then 7.2 parts of sodium nitrite was added. This solution was added dropwise to 200 parts of 5% hydrochloric acid at 0 to 10 ° C. over 30 minutes, followed by stirring at 10 ° C. or lower for 1 hour to carry out diazotization reaction to prepare a diazo reaction liquid. Meanwhile, 23.1 parts of 2- (sulfopropoxy) aniline is dissolved in 130 parts of water while adjusting the pH to 7 with sodium hydroxide, and 10.4 parts of sodium bisulfite and 8.6 parts of 35% formalin are used.
  • a methyl- ⁇ -sulfonic acid derivative was obtained by a conventional method.
  • the obtained methyl- ⁇ -sulfonic acid derivative was added to the previously prepared diazo reaction liquid and stirred at 0 to 15 ° C. and pH 2 to 4 for 24 hours.
  • the reaction solution was adjusted to pH 11 with sodium hydroxide, stirred at 80 to 95 ° C. for 5 hours while maintaining the same pH, further salted out by adding 100 parts of sodium chloride, and the precipitated solid was separated by filtration. 100 parts of an azo compound represented by the following formula (9) was obtained as a wet cake.
  • the obtained reaction solution was cooled to 20 to 25 ° C., 800 parts of acetone was added to the reaction solution, and the mixture was stirred at 20 to 25 ° C. for 1 hour.
  • the precipitated solid was separated by filtration to obtain 50.0 parts of a wet cake.
  • the wet cake was dried with a hot air dryer at 80 ° C. to obtain 13.5 parts of a sodium salt ( ⁇ max: 383.5 nm) of the water-soluble azo compound of the present invention represented by the following formula (10).
  • Example 2 In the same manner as in Example 1 except that 14.0 parts of 2-aminoethanol in Example 1 (Step 2) were used instead of 14.0 parts of methylamine (40% aqueous solution), the following formula (11) 12.5 parts ( ⁇ max: 383.0 nm) of the sodium salt of the water-soluble azo compound of the present invention represented was obtained.
  • Example 3 This is represented by the following formula (12) in the same manner as in Example 1 except that 110.0 parts of t-butylamine is used instead of 18.3 parts of 2-aminoethanol in Example 1 (Step 2). 5.0 parts ( ⁇ max: 387.0 nm) of the sodium salt of the water-soluble azo compound of the invention was obtained.
  • Example 4 It is represented by the following formula (13) in the same manner as in Example 1 except that 29.1 parts of 2-furfurylamine is used in place of 18.3 parts of 2-aminoethanol in Example 1 (Step 2). 14.0 parts ( ⁇ max: 388.5 nm) of the sodium salt of the water-soluble azo compound of the present invention was obtained.
  • Example 5 The present invention represented by the following formula (14) in the same manner as in Example 1 except that 40.0 parts of iminodiacetic acid was used instead of 18.3 parts of 2-aminoethanol in Example 1 (Step 2). 12.0 parts ( ⁇ max: 399.0 nm) of a water-soluble azo compound sodium salt was obtained.
  • Example 6 to 10 (A) Preparation of ink
  • the ink composition of the present invention was obtained by mixing to obtain a solution.
  • the obtained ink composition was filtered through a 0.45 ⁇ m membrane filter to remove impurities, and a test ink was prepared.
  • the pH of the test ink was in the range of 8.0 to 9.5.
  • surfactant trade name Surfinol RTM 104PG50 manufactured by Nissin Chemical Co., Ltd. was used.
  • Preparation of each ink using the compounds obtained in Examples 1 to 5 is referred to as Examples 6 to 10, respectively.
  • Comparative Example 1 Comparative inks were prepared in the same manner as in Examples 6 to 10 except that the compound described in Example 25 of Patent Document 1 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 1.
  • the structural formula of the compound used in Comparative Example 1 is shown in the following formula (15).
  • Comparative Example 2 Comparative inks were prepared in the same manner as in Examples 6 to 10 except that the coloring matter described in Example 2 of Patent Document 2 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 2.
  • the structural formula of the compound used in Comparative Example 2 is shown in the following formula (16).
  • Comparative Example 3 Comparative inks were prepared in the same manner as in Examples 6 to 10 except that the coloring matter described in Example 1 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 3.
  • the structural formula of the compound used in Comparative Example 3 is shown in the following formula (17).
  • Glossy paper 1 Canon Inc.
  • Product name: Glossy Pro Platinum Grade (PT-101) Glossy paper 2 manufactured by Canon Inc.
  • Product name: Glossy Gold (GL-101) Glossy paper 3 Seiko Epson Corporation, trade name: Photographic paper Krispia (high gloss) Glossy paper 4: Hewlett-Packard Company, product name: Advanced Photo Paper (Q8861A) Glossy paper 5: manufactured by Brother Co., Ltd., trade name: photographic paper (BP71GA4)
  • the reflection density was measured for the portion where the reflection density D value of the recorded matter before the test was closest to 1.0. Saturation (C * value) and reflection density (Dy value) were measured at the highest gradation. A colorimetry system (trade name SpectroEye RTM , manufactured by X-rite) was used for the measurement of saturation and reflection density. Colorimetry was performed under the conditions of DIN, a viewing angle of 2 degrees, and a light source D65 as a density standard. Various test methods for recorded images and evaluation methods for test results are described below.
  • Comparative Example 1 shows extremely inferior results to Examples 6 to 10 for any glossy paper with respect to the above yellow printing density (Dy value), and Comparative Examples 2 and 3 show Example 6. A result inferior to 10 was shown.
  • Comparative Example 1 showed extremely inferior results to Examples 6 to 10 in any glossy paper in saturation (C * value). Further, Comparative Example 2 showed results inferior to Examples 6 to 10.
  • Comparative Example 1 shows results that are extremely inferior to each of the glossy papers in yellow printing density (Dy value) and saturation (C * value), and Comparative Example 2 In any glossy paper, the yellow printing density (Dy value) and saturation (C * value) were inferior to those of the examples.
  • Comparative Example 3 is relatively good in glossy papers 2, 3, and 5 in saturation (C * value), but inferior to each of Examples in glossy papers 1 and 4, and yellow printing density (Dy value) ) Showed inferior results to each of the examples in any glossy paper. In contrast, each example showed excellent results for all glossy papers in the saturation (C * value) and yellow printing density (Dy value) of the recorded matter.
  • the water-soluble azo compound of the present invention and the ink composition of the present invention containing the compound have hues with high sharpness in many types of glossy paper as compared with conventional dyes. It can be seen that the yellow print density value is high and the color developability is excellent regardless of the type of glossy paper.
  • the water-soluble azo compound of the present invention which is a yellow pigment
  • the yellow ink composition of the present invention containing the same provide a recorded image with high color development and high saturation. Therefore, the compound and the ink composition containing the compound are very useful for various recording applications, particularly for inkjet recording applications.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Abstract

Le but de la présente invention est de fournir : un colorant jaune soluble dans l'eau (composé) qui est hautement soluble dans l'eau, a des propriétés élevées de développement de la couleur, et donne des images imprimées ayant un excellent chroma; et une composition d'encre jaune qui contient le colorant et est destinée à l'utilisation dans divers types d'impression, en particulier, l'impression par jet d'encre. Le colorant est un composé azoïque soluble dans l'eau représenté par la formule (1) ou un sel de celui-ci. La composition d'encre, qui contient le composé ou le sel, a des propriétés élevées de développement de la couleur, a un chroma et une teinte qui sont appropriés pour l'impression par jet d'encre, donne une matière imprimée ayant des propriétés élevées de solidité des couleurs de diverses sortes, et donne des images enregistrées qui sont excellentes en termes de stabilité au stockage ou similaires. Dans la formule (1), x est un entier de 2-4, et le groupe A représente un groupe amino représenté par n'importe laquelle des formules (2) à (6). Dans la formule (2), w est un entier de 2-6. Dans la formule (3), v est un entier de 1-3.
PCT/JP2011/080063 2010-12-27 2011-12-26 Composé azoïque soluble dans l'eau ou sel de celui-ci, composition d'encre, et objet coloré WO2012090933A1 (fr)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
WO2014192932A1 (fr) * 2013-05-31 2014-12-04 日本化薬株式会社 Composé azoïque soluble dans l'eau ou son sel, composition d'encre, et article coloré
JP2018127587A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 水溶性アゾ化合物又はその塩、インク組成物及び着色体
JP2018127584A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 水溶性アゾ化合物又はその塩、インク組成物及び着色体
JP2018127588A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 水溶性アゾ化合物又はその塩、インク組成物及び着色体
JP2018127591A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 アゾ化合物又はその塩、インク組成物及び着色体
JP2018127589A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 水溶性アゾ化合物又はその塩、インク組成物及び着色体

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JPH04233975A (ja) * 1990-07-26 1992-08-21 Imperial Chem Ind Plc <Ici> 陰イオン性アゾ化合物
JP2006152264A (ja) * 2004-10-26 2006-06-15 Nippon Kayaku Co Ltd 水溶性アゾ化合物、インク組成物および着色体
WO2009066412A1 (fr) * 2007-11-20 2009-05-28 Nippon Kayaku Kabushiki Kaisha Composé azoïque hydrosoluble ou sel de celui-ci, composition d'encre et corps coloré
WO2010125903A1 (fr) * 2009-04-28 2010-11-04 日本化薬株式会社 Composé azoïque hydrosoluble ou son sel, composition d'encre et article coloré
WO2010146994A1 (fr) * 2009-06-17 2010-12-23 日本化薬株式会社 Composé azoïque hydrosoluble ou sel de celui-ci, composition d'encre et corps coloré

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JPH04233975A (ja) * 1990-07-26 1992-08-21 Imperial Chem Ind Plc <Ici> 陰イオン性アゾ化合物
JP2006152264A (ja) * 2004-10-26 2006-06-15 Nippon Kayaku Co Ltd 水溶性アゾ化合物、インク組成物および着色体
WO2009066412A1 (fr) * 2007-11-20 2009-05-28 Nippon Kayaku Kabushiki Kaisha Composé azoïque hydrosoluble ou sel de celui-ci, composition d'encre et corps coloré
WO2010125903A1 (fr) * 2009-04-28 2010-11-04 日本化薬株式会社 Composé azoïque hydrosoluble ou son sel, composition d'encre et article coloré
WO2010146994A1 (fr) * 2009-06-17 2010-12-23 日本化薬株式会社 Composé azoïque hydrosoluble ou sel de celui-ci, composition d'encre et corps coloré

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014192932A1 (fr) * 2013-05-31 2014-12-04 日本化薬株式会社 Composé azoïque soluble dans l'eau ou son sel, composition d'encre, et article coloré
JP2018127587A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 水溶性アゾ化合物又はその塩、インク組成物及び着色体
JP2018127584A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 水溶性アゾ化合物又はその塩、インク組成物及び着色体
JP2018127588A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 水溶性アゾ化合物又はその塩、インク組成物及び着色体
JP2018127591A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 アゾ化合物又はその塩、インク組成物及び着色体
JP2018127589A (ja) * 2017-02-10 2018-08-16 日本化薬株式会社 水溶性アゾ化合物又はその塩、インク組成物及び着色体

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