WO2013075286A1 - Binuclear anthracene pyridine sulphonic acid compound or salt thereof and preparation process and use thereof - Google Patents

Binuclear anthracene pyridine sulphonic acid compound or salt thereof and preparation process and use thereof Download PDF

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Publication number
WO2013075286A1
WO2013075286A1 PCT/CN2011/082623 CN2011082623W WO2013075286A1 WO 2013075286 A1 WO2013075286 A1 WO 2013075286A1 CN 2011082623 W CN2011082623 W CN 2011082623W WO 2013075286 A1 WO2013075286 A1 WO 2013075286A1
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Prior art keywords
salt
compound
sulfonic acid
formula
dinuclear
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PCT/CN2011/082623
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French (fr)
Chinese (zh)
Inventor
彭孝军
吴金河
樊江莉
孟凡明
宋锋玲
孙世国
张蓉
王静月
龙志
王力成
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大连理工大学
大连福思达专用化学有限公司
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Priority to PCT/CN2011/082623 priority Critical patent/WO2013075286A1/en
Publication of WO2013075286A1 publication Critical patent/WO2013075286A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
    • C09B1/34—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups sulfonated
    • C09B1/343—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups sulfonated only sulfonated in the anthracene nucleus
    • 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
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
    • C09B5/14—Benz-azabenzanthrones (anthrapyridones)

Definitions

  • the present invention relates to a structure of a class of dinuclear pyridinone sulfonic acid compounds, a process for synthesizing such a binuclear pyridinone sulfonic acid compound, and a magenta ink containing such a binuclear pyridinone sulfonic acid compound for ink jet printing. Background technique
  • the inkjet printing method is one of the typical color recording methods. Since the head does not come into contact with the material to be recorded, it is quiet without sound, and it is easy to be miniaturized, speeded up, and colored, and has been rapidly developed in recent years.
  • inks for ink jet printing are generally produced by dissolving a water-soluble dye in an aqueous medium and adding a water-soluble organic solvent which prevents clogging of the pen tip and the ink jet nozzle ink.
  • These inks are required to have a high-density printed image, a tip or nozzle that does not block, a good drying property on a book recording material, a small penetration, and excellent storage stability.
  • the formed image must have water resistance and light resistance. Fastness to sex, moisture resistance, etc.
  • ink water resistance Usually, the surface of the substrate is adsorbed by porous silica, cationic polymer, alumina sol or special ceramic.
  • the dye is coated on the paper surface together with these organic or inorganic particles and PVA resin. The ground is improved.
  • moisture resistance When the printed image is stored in a high humidity environment, the penetration of the dye in the recorded material is fast, if there is penetration of the dye, especially in the case of high photo coloring requirements, Will significantly reduce the image quality.
  • light resistance The four primary colors of yellow, magenta, cyan, and black have the weakest light resistance, and this improvement has become an important issue.
  • ozone gas is a main substance for promoting oxidation and fading of ink-jet printed images. Therefore, improvement of ozone-resistant gas properties is also an important issue in improving light resistance.
  • the molecular skeleton of the dye for magenta used in the inkjet ink is represented by an oxazepine type rhodamine dye and an azo type dye coupled by H acid.
  • the rhodamine dye is excellent in color tone and vividness, but its light resistance is extremely poor.
  • the H-acid azo dye although the color and water resistance are good, the light resistance, the ozone resistance, and the vividness are insufficient, especially compared with the cyan dye and the azo yellow dye represented by copper phthalocyanine. , light resistance is still insufficient.
  • the present invention has been made in order to solve the above problems, and it has been found that an sulfonic acid compound of anthrapyridone can solve the above problems.
  • the present invention first provides a class of dinuclear anthrapyridone sulfonic acid compounds or salts thereof having the structure of formula I:
  • L is a linking group
  • R 7 is a CM group
  • n is an integer of 0-2;
  • n is an integer from 0-3.
  • the binuclear pyridinone sulfonic acid compound or a salt thereof according to the present invention is - (E-1 to E-10) or a salt thereof:
  • the above-mentioned dinuclear pyridinium sulfonate compound or a salt thereof according to the present invention wherein the salt is a lithium salt, a sodium salt, a potassium salt, an ammonium salt or an organic ammonium salt of the corresponding dinuclear pyridone sulfonic acid compound.
  • the organic ammonium salt cation has a structure of the general formula N + R 3 R4R 5 R 6 wherein R 3 , R 5 , R 6 are each independently selected from the group consisting of 11, C M8 fluorenyl, cyclohexyl, CH 2 CH 2 OH and benzyl.
  • the salt of the dinuclear pyridone sulfonic acid compound is a lithium salt, a sodium salt, a potassium salt, an ammonium salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, a single of the corresponding dinuclear pyridone sulfonic acid compound.
  • the salt is a lithium, sodium or ammonium salt of the corresponding dinuclear pyridone sulfonic acid compound.
  • Another object of the present invention is to provide a process for producing the above-described dinuclear pyridinone sulfonic acid compound of the present invention or a salt thereof, comprising the steps of:
  • the organic solvent is xylene, diethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene or a mixed solvent of DMF and DMSO in a volume ratio of 3:1;
  • a compound of the formula VI is prepared by reacting a compound of the formula V with a cyanuric chlorination ratio of 1:1 in an anionic emulsifier with a 25 % aqueous sodium hydroxide solution at a pH of 3-4 for 3 hours.
  • R is selected from the group consisting of: OH, O(C 6 H 5-m )(CO 2 H) m S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H, O(C 6 H 5- m )(SO 3 H) m , O(C 10 H 9-m )(CO 2 H) m , O(C 10 H 9-m )(SO 3 H) m , leg 2 , grass 7 ) 2 , SH , SR 7 , NH(C 6 H 5-m )(CO 2 H) m , NH(C 6 H 5-m )(SO 3 H) m , NH(C 10 H 9-m )(CO 2 H) m , NH(C 10 H 9-m )(SO 3 H) m , S(C 6 H 5-m )(CO 2 H) m , S(C 6 H 5-m )(SO 3 H) m , S(C 6 H 5-m )(CO
  • p, q are integers from 1 to 18.
  • a further object of the present invention is to provide a magenta ink composition comprising the above-described dinuclear pyridone sulfonic acid compound of the present invention or a salt thereof.
  • the magenta ink composition contains water and a water-soluble organic solvent.
  • the mass percentage of the dinuclear pyridone sulfonic acid compound in the magenta ink composition is 0.1 to 20%.
  • the mass percentage of inorganic impurities in the magenta ink composition does not exceed 1% of the total mass of the non-solvent component.
  • Another object of the present invention is also to provide the use of the magenta ink combination of the present invention described above in ink jet printing.
  • the present invention introduces an electron-absorbing water-soluble group sulfonic acid group on the anthracene ring of the dinuclear pyridone, which has not appeared in the prior art in the prior art, and can not only reduce the electron cloud density of the molecule, but also improve the light resistance. Oxidation and ozone oxidation, and can improve the solubility of the dye, enhance the stability of the dye in the ink; and the two dye precursors can improve the water resistance of the dye image.
  • the industrial bromate blue dye is used as a starting material, the sulfonic acid compound generally used in the prior art is avoided, the reaction step is small, the process flow is short, and the raw materials are inexpensive, and the compound represented by the formula (I) of the present invention and
  • the magenta ink composition prepared from the salt exhibits a sharp color and an extremely high color tone on the ink jet recording paper, and is excellent in water solubility, and has good filterability to the filter in the production process of the ink composition.
  • the printed matter of the red ink set of the inkjet recording article containing the anthrapyridone compound of the present invention does not select a material to be recorded (paper, film, etc.) to provide an ideal magenta tone, and the magenta of the present invention
  • the ink composition faithfully restores the color tone of the color tone of the photo tone, and is light-resistant and resistant even when printed on a surface coated with inorganic fine particles such as inkjet paper (film) for photo quality.
  • the fastness of ozone, moisture resistance, etc. is good, and the long-term preservation of images is stable.
  • L is a linking group, preferably -NH(CH 2 ) p NH -, -S(CH 2 ) q S- or compound L
  • p and q are integers from 1 to 18, preferably integers from 2 to 6.
  • R n R 2 are each independently selected from the group consisting of: OH, O(C 6 H 5-m )(CO 2 H) m , S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H, O ( C 6 H 5-m )(SO 3 H) m , O(C 10 H 9-m )(CO 2 H) m , O(C 10 H 9-m )(SO 3 H) m , NH 2 , grass 7 ) 2 , SH, SR 7 , NH(C 6 H 5-m )(CO 2 H) m , NH(C 6 H 5-m )(SO 3 H) m , NH(C 10 H 9-m )(CO 2 H) m , NH( C 10 H 9-m )(SO 3 H) m , S(C 6 H 5-m )(CO 2 H) m , S(C 6 H 5-m )(SO 3 H) m , S(C 6
  • R 7 is a CM fluorenyl group; n is an integer of 0-2; m is an integer of 0-3.
  • the sum is the same group selected from the group consisting of: o-OC 6 H 5 (CO 2 H) 2 , S(CH 2 ) 3 SO 3 H and p-OC 6 H 5 SO 3 H.
  • mercapto refers to a straight or branched fluorenyl group.
  • a sulfonic acid group is introduced on the core of the substituted 4-aminopyridinone to increase the water solubility; and the two pyridone sulfonic acid compound cores are further connected by a linking group L to improve water resistance.
  • the compound of the formula I is in practical use, usually in the form of a cationic salt, which is a lithium salt, a sodium salt, a potassium salt, an ammonium salt or an organic ammonium salt of the corresponding dinuclear pyridone sulfonic acid compound,
  • the organic ammonium salt cation has a structure of the general formula N + R 3 R4R 5 R 6 wherein R 3 , R 5 , R 6 are each independently selected from the group consisting of 11, C M8 fluorenyl, cyclohexyl, CH 2 CH 2 OH and benzyl. base.
  • the salt is a lithium salt, a sodium salt, a potassium salt, an ammonium salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, a monoisopropanol of the corresponding dinuclear pyridone sulfonic acid compound.
  • An amine salt, a diisopropanolamine salt or a triisopropanolamine salt is most preferred.
  • the method for preparing a dinuclear pyridinone sulfonic acid compound of the formula I is cyclized in an organic solvent to form a compound of the formula IV, and then sulfonated and hydrolyzed to form an amino group-containing compound.
  • Formula V which then forms intermediate VI with cyanuric chloride, is then reacted with compound RH to form compound of formula VII, and finally joined by a linker HLH to form compound of formula I.
  • the salt is then converted to form a salt.
  • the reaction conditions of the reaction of the blue sulfonic acid compound (formula III) with benzoyl acetate to form compound IV are: 1 compound III and benzoyl acetate (such as a Ester, ethyl ester, propyl ester, isopropyl ester)
  • the reaction is carried out at a molar ratio of 1: 2 to 5 in an organic solvent at 175 to 180 °C.
  • the molar ratio of the compound III to the benzoyl acetate is preferably 1:3.
  • the benzoyl acetate is preferably exemplified by a methyl ester, an ethyl ester, a propyl ester or an isopropyl ester.
  • the solvent is a mixed solvent of a high boiling organic solvent and DMSO, and these organic solvents are preferably xylene, diethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene or DMF.
  • the ring-forming reaction of formula III is preferably carried out in the presence of a base selected from the group consisting of sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, lithium carbonate, lithium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate, phosphoric acid.
  • a base selected from the group consisting of sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, lithium carbonate, lithium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate, phosphoric acid.
  • Sodium carbonate and sodium hydrogencarbonate are preferred.
  • the molar ratio of the base added to the compound III is
  • the ring-forming reaction of formula III can increase the temperature of the reaction under pressure or vacuum, optionally from 0.5 to 5 atmospheres.
  • the ring-forming reaction of formula III should be carried out under monitoring, using liquid chromatography or thin layer chromatography to control the disappearance of the blue hydrazine dye compound III as the end of the reaction.
  • the ring-forming reaction of formula III uses a water separator to separate the formed water and ethanol from the reflux condenser to promote completion of the reaction.
  • an organic solvent with a low boiling point of 30 to 150 ° C is advantageous for precipitation.
  • the optional solvents include methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, dioxane, and dichloroformamidine.
  • Sulfonated hydrolysis reaction of the compound of the formula IV In the sulfonation reaction of the compound of the formula IV with fuming sulfuric acid, the content of sulfur trioxide in the fuming sulfuric acid is 5 to 15%, preferably 8 to 13%, and most preferably 9 to 12%. .
  • the reaction can be controlled by phase chromatography or thin layer chromatography to control the endpoint of the reaction.
  • the sulfonated product was poured into ice water with stirring, and the reaction was hydrolyzed at 40 to 60 ° C for 0.1 to 2 hours. Then, ammonium chloride or sodium chloride is added for multiple salting out, cooled, and filtered to obtain a compound of the formula V.
  • the compound of the formula I can be salted by a conventional method, for example, by reacting with potassium hydroxide, lithium hydroxide, aqueous ammonia or an organic amine to obtain a corresponding potassium salt, lithium salt, ammonium salt or organic ammonium salt.
  • a conventional method for example, by reacting with potassium hydroxide, lithium hydroxide, aqueous ammonia or an organic amine to obtain a corresponding potassium salt, lithium salt, ammonium salt or organic ammonium salt.
  • lithium salts, sodium salts, potassium salts, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, diisopropanolamine salts or triisopropanolamine salts are preferred.
  • a lithium salt, a sodium salt or an ammonium salt is particularly preferred.
  • the mass percentage of the inorganic impurities does not exceed 1% of the total mass of the non-solvent component, and the dye may be desalted by a general method such as a high pressure reverse osmosis membrane. .
  • the magenta ink composition of the present invention is a composition obtained by dissolving a compound of the formula I or a salt thereof in water or an aqueous solvent.
  • the content of the dinuclear pyridone compound in the ink composition is generally 0.1 to 20%, preferably 1 to 15%, particularly preferably 2 to 10%.
  • the magenta ink composition of the present invention may contain 0 to 30% of a water-soluble organic solvent and 0 to 5% by weight of an ink preparation agent, respectively.
  • the rest is water.
  • the water-soluble organic solvent used in the present invention includes: methanol, ethanol, n-propanol, isopropanol, n-butanol, Isobutanol, sec-butanol, tert-butanol, etc.
  • N N-dimethylformamide or amide of carboxylic acid such as N,N-dimethylacetamide
  • 2-pyrrolidone N- a lactam such as methyl-2-pyrrolidone
  • a cyclic nitrogen-containing solvent such as 1,3-dimethylmorpholin-2-one or 1,3-dimethylhexahydropyrimidin-2-one
  • acetone A Ketone or keto alcohol
  • cyclic ether such as tetrahydrofuran or dioxan
  • ethylene glycol 1,2- or 1,3-propanediol, 1 , 2- or 1,4-butanediol, 1,6-hexanediol.
  • Monomers, oligomers or polyfluorenes having C 2 -6 fluorenylene units such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiol, polyethylene glycol, polypropylene glycol a diol or a thioglycol; a polyhydric alcohol (triol) such as glycerin or hexamethylene-1,2,6-triol; ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, Diethylene glycol monobutyl ether; d_ 4 mercapto ether of a polyhydric alcohol such as diethylene glycol monoethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; ⁇ -butyrolactone or dimethyl sulfoxide Wait.
  • a polyhydric alcohol such as glycerin or hexamethylene-1,2,6-
  • water-soluble organic solvents may be used singly or in combination.
  • the ink preparation agent include antiseptic and antifungal agents, ⁇ adjusters, chelating agents, rust preventives, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye dissolvers, surfactants, and the like. .
  • antiseptic and antifungal agent examples include, for example, organic sulfurs, organic nitrogen sulfurs, organic halogens, haloallylsulfones, iodopropynes, anthraquinone-sulfonylsulfurs, nitriles, pyridines, and 8 -hydroxyquinoline, benzothiazoles, isothiazolines, dithiols, pyridine oxides, nitropropenes, organotins, phenols, quaternary ammonium salts, triazines, thiadiazines Compounds such as anilides, amantadines, dithiocarbamates, indanones, benzyl bromide, and inorganic salts.
  • organic halogen compound examples include, for example, sodium pentachlorophenol
  • examples of the pyridine oxide compound include, for example, 2-pyridinethiol-1-oxide
  • examples of the inorganic salt compound include, for example, anhydrous acetic acid.
  • Examples of the isothiazoline compound include, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl 4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one Calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, and the like.
  • Examples of other antiseptic and antifungal agents include sodium sorbate and sodium benzoate.
  • the ⁇ adjusting agent is not affected by the adverse effects of the conditioned ink, and any substance can be used as long as the ⁇ ⁇ of the ink can be controlled within the range of 8.0 to 11.0.
  • decylamines such as diethanolamine and triethanolamine
  • hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide
  • ammonium hydroxide or aqueous ammonia or lithium carbonate, sodium carbonate, and potassium carbonate.
  • An alkali metal carbonate is preferred.
  • chelating agent examples include sodium edetate, sodium nitrotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium urethane diacetate, and the like.
  • Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and the like.
  • Examples of the water-soluble ultraviolet absorber include, for example, a sulfonated benzophenone or a sulfonated benzotriazole.
  • Examples of the water-soluble high-concentration compound include polyvinyl alcohol, a cellulose derivative, a polyamine, a polyimine, and the like.
  • Examples of the dye solubilizing agent include urea, ⁇ -caprolactam, diethyl carbonate and the like.
  • surfactant examples include anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants.
  • anionic surfactant examples include, for example, a mercaptosulfocarboxylate, an ⁇ -olefinsulfonate, a polyoxyethyleneetherether acetate, a hydrazinoylamino acid, and a salt thereof.
  • ⁇ -acylmethyltaurate citronellyl soap, castor oil sulfate, lauryl sulfate, nonylphenol phosphate, thiol phosphate, decyl propyl sulfonate, Diethyl sulfosuccinate, diethylhexyl sulfosuccinic acid, dioctyl sulfosuccinate, and the like.
  • the cationic surfactant include a 2-vinylpyridine derivative and a poly-4-vinylpyridine derivative.
  • amphoteric surfactant examples include, for example, lauryl dimethylaminoacetic acid betaine, 2-mercapto-indenyl-carboxymethyl-hydrazine-hydroxyethylimidazoline-betaine, and coconut oil fatty acid amide propyl Methylaminoacetic acid betaine, other imidazoline derivatives of polyoctyl polyaminoethylglycine, and the like.
  • nonionic surfactant include, for example, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene octylphenyl group.
  • Ethers such as ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene decyl ether; polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene urethane Fatty acid ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, Esters such as polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3 a decynediol such as 6-diol or 3,5-dimethyl-1-hexyne-diol (for example, Surfynol 104, 82, 465, Olfme STG, etc., manufactured by Nisshin Chemical Co., Ltd.).
  • These ink modulating agents can be used singly or
  • the compound of the formula I or a salt thereof is dissolved in water or the above aqueous solvent, and if necessary, it can be produced by dissolving together with the above-mentioned ink preparation agent or the like.
  • the order of dissolution of each component is not particularly limited.
  • the dye may be dissolved in water or the above aqueous solvent in advance, and dissolved by adding an ink preparation agent. After the dye is dissolved in water, an aqueous solvent or an ink preparation agent may be added to dissolve the dye. It can also be different from this order. Further, an aqueous ink or an ink preparation agent may be added to a solution obtained by subjecting the reaction liquid containing the dye or the solution containing the dye to a desalting treatment to prepare an ink composition.
  • the water to be used is preferably ion-exchanged water or deionized water having less impurities such as distilled water.
  • a filter or the like is used for precision filtration and removal of inclusions.
  • the pore size of the filter for precision filtration is usually from 1 ⁇ m to 0.1 ⁇ m, preferably from 0.8 ⁇ m to 0.2 ⁇ m.
  • the magenta ink composition of the water-soluble dinuclear pyridone sulfonic acid compound of the present invention is suitable for use in stamping, copying, marking, taking, drawing, stamping or printing, particularly for ink jet printing.
  • the advantage is that the resulting image is Water, sunlight, ozone and friction have excellent resistance and can also be used for color matching, especially for black.
  • the coloring matter of the present invention is a dye represented by the above compound of the formula I of the present invention or a salt thereof, and can be used for coloring a plurality of substrates, such as: paper, fiber or cloth (cellulose, nylon, wool, etc.), leather, filter.
  • the substrate for a color filter or the like is not limited thereto.
  • the coloring method may be, for example, a method such as a dip dyeing method, a printing method, a screen printing method, or the like, or an ink jet printing method, and an ink jet printing method is preferred.
  • Examples of the substrate to be recorded which can be applied to the ink jet printing method of the present invention include sheets for information transmission such as paper and film, fibers, leather, and the like.
  • sheets for information transfer surface treatment is usually required, and an ink absorbing layer is provided in these substrates.
  • the ink absorbing layer is, for example, a polymer such as a cation which is impregnated or coated on the substrate, and the coating layer further contains porous silica, alumina sol or special ceramics, etc., and these white inorganic substances are polyvinyl alcohol or polyethylene.
  • a hydrophilic polymer such as pyrrolidone is applied together to the surface of the substrate.
  • Sheets provided with these ink absorbing layers are generally referred to as inkjet papers/films or glossy papers/films, such as: professional glossy paper, top gloss paper, mat gloss paper (made by Canon), photo paper. Gloss, mat paper, ultra-thin special glossy film (made by Epson), high-quality glossing paper, high-quality glossy film, glossy paper (made by HP), etc.
  • plain paper can of course be used.
  • an image is printed on a substrate coated with a porous white inorganic substance, and the discoloration caused by ozone is increased.
  • the aqueous magenta ink composition of the present invention is excellent in gas resistance, such a base is The printing of the material can have a special effect.
  • porous white inorganic substance examples include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, and calcium silicate.
  • inkjet printing of the present invention in addition to the usual yellow, cyan ink composition, there are also a green ink composition, an orange ink composition, a blue (or purple) ink composition, and a magenta ink combination of the present invention.
  • a black ink composition or the like may be used in combination as necessary.
  • the ink compositions of the respective colors are injected into respective ink cartridges and used in a predetermined position of the ink jet printer.
  • Examples of the ink jet printer include a piezoelectric printer or a foaming printer that generates bubbles by heating.
  • the water-based magenta ink composition of the present invention is a vivid magenta color, and particularly has a high vivid color tone in ink-jet glossy paper, and the recorded image has high fastness and high safety to the human body.
  • the ink composition of the present invention does not precipitate or separate during storage. Moreover, when the ink of the present invention is used in ink jet printing, the head is not blocked. The ink of the present invention does not undergo physical property changes even if it is used by a continuous ink jet printer for a long period of time or intermittent use.
  • a 10% aqueous NaOH solution was added to maintain the pH at 2.7 to 3, and it was carried out at 25 to 30 ° C for 3 hours to obtain a reaction liquid of a condensation reaction intermediate E1-C1 2 (expressed in a free acidic form).
  • the maximum absorption wavelength in water is 520 nm.
  • the ice and aqueous sodium hydroxide solution were continuously added, the pH was maintained at 9.0 ⁇ 0.3, and the temperature was raised to 27 to 30 ° C, and the reaction was carried out at this temperature and pH for 1 hour, and then at 40 to 45 ° C for 1 hour. After the completion of the reaction, water was added to adjust the amount of the liquid to about 350 parts, and the insoluble matter was removed by filtration.
  • Compound E1-C1 2 was prepared according to the steps (1) - (3) in Example 1.
  • the ice and aqueous sodium hydroxide solution were continuously added, the pH was maintained at 9.0 ⁇ 0.3, and the temperature was raised to 27 to 30 ° C, and the reaction was carried out at this temperature and pH for 1 hour, and then at 40 to 45 ° C for 1 hour. Counter After completion, water was added to adjust the liquid amount to about 350 parts, and the insoluble matter was removed by filtration.
  • the compound E-3 can be prepared by replacing sodium 5-hydroxyisophthalate in the step (4) of the first embodiment with sodium mercaptopropanesulfonate.
  • Compound E-7 can be prepared by replacing ethylenediamine in step (5) of Example 1 with ethanedithiol.
  • Compound E-4 can be prepared by replacing ethylenediamine in step (5) of Example 1 with compound L.
  • Compound E-5 can be prepared by replacing ethylenediamine in step (5) of Example 2 with compound L.
  • Compound E-6 can be prepared by replacing sodium 5-hydroxyisophthalate in step (4) with sodium decyl propane sulfonate and ethylenediamine in step (5) with compound L.
  • Compound E-8 can be prepared by replacing ethylenediamine in step (5) of Example 2 with ethanedithiol.
  • Compound E-9 can be prepared by replacing ethylenediamine in step (5) of Example 2 with hexamethylenedithiol.
  • Compound E-10 can be prepared by replacing ethylenediamine in step (5) of Example 2 with hexamethylenediamine.
  • Example 3 Magenta ink composition containing compound
  • compositions shown in the following Table were separately prepared and filtered through a 0.45 m membrane filter to obtain an aqueous magenta ink composition of the present invention. Further, ion-exchanged water and triethanolamine were added to adjust the pH of the ink composition to 8 to 10 and the total amount to 100 parts by weight.
  • the selected dye and the comparative mononuclear dye Dyel, the commercial dye C.I. Reactive Red 180 hydrolyzed derivative (abbreviated as Reactive Red 180) and C.I. Direct Red 227 were respectively prepared into comparative ink compositions. These ink compositions were used for ink jet printing, and evaluation of printed images was performed.
  • Component content (parts by weight)
  • the binuclear pyridinone dye of the invention (100%) 6
  • the remaining amount of deionized water is up to 100 parts by weight (B) Inkjet printer:
  • a high-light photographic paper manufactured by Epson Co., Ltd.
  • an ink-receiving layer containing a porous white inorganic material was subjected to inkjet printing using an ink jet printer (Epson Model 270 printer manufactured by Epson Co., Ltd.).
  • the print sample of the image has a density stage.
  • the test piece of the glossy paper manufactured by Canon and the glossy paper made by Epson was used, and the Xenon lamp weather resistance meter Ci400 (trade name; manufactured by ATLAS) was used under the conditions of humidity 60% RH and temperature 24 °C. Irradiation was carried out for 50 hours at an illuminance of O.36 W/m 2 , and the color difference ( ⁇ ) before and after the test was measured.
  • Color difference ( ⁇ ) is the value of each L*, a*, b* before and after the measurement test by the above-mentioned color measurement system (Schlab: GRETAG), and before and after the test of each value of L*, a*, b*
  • the difference is obtained by the following formula:
  • ⁇ E ((L* difference) 2 + (a difference of a*) 2 + (difference of b*) 2 ) 1/2 .
  • the glossy paper manufactured by Canon Inc. was placed in an ozone concentration of 40 ppm, a humidity of 60% RH, and a temperature of 24 ° C for 6 hours using an ozone weather resistance meter (manufactured by the company).
  • the color difference ( ⁇ ) before and after the test obtained in the same manner as in the above (2) was evaluated in three levels according to the following criteria:
  • test piece of the glossy paper manufactured by Canon and the glossy paper made by Epson was placed in a constant temperature and humidity apparatus (manufactured by Applied Technology Co., Ltd.) at 50 ° C, 90% RH for 168 hours to visually observe.
  • the exudation property before and after the test was judged and evaluated in three levels according to the following criteria.
  • the dinuclear pyridone sulfonic acid dye of the present invention has extremely excellent stability, light resistance, ozone resistance and moisture resistance as an inkjet dye.

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Abstract

Disclosed is a binuclear anthracene pyridine sulphonic acid compound of general formula I or a salt thereof. Magenta ink compositions prepared from the compound and the salt thereof appear fresh, have a bright tone on ink-jet recording paper, excellent water solubility, and good filterability for the membrane filter during the production of ink compositions. Furthermore, the ink composition using the compound of the present invention does not have any precipitated crystals, physical changes, or colour change after a long storage period, and has good stability when stored. Printouts using the magenta ink composition of the present invention have no special requirements as regards recording materials, can faithfully reproduce and present the tone of a coloured image of photographic tone, and have good fastness, such as resistance to light, ozone, and damp, and the image can be kept stable for a long time.

Description

双核蒽吡啶酮磺酸化合物或其盐、 其制备方法及应用  Dinuclear pyridinone sulfonic acid compound or salt thereof, preparation method and application thereof
技术领域 Technical field
本发明涉及一类双核蒽吡啶酮磺酸化合物的结构、 这类双核蒽吡啶酮磺酸化合物 的合成方法、 含有该类双核蒽吡啶酮磺酸化合物的品红墨水用于喷墨打印。 背景技术  The present invention relates to a structure of a class of dinuclear pyridinone sulfonic acid compounds, a process for synthesizing such a binuclear pyridinone sulfonic acid compound, and a magenta ink containing such a binuclear pyridinone sulfonic acid compound for ink jet printing. Background technique
喷墨打印方法是典型的彩色记录方法之一。 由于喷头不与被记录材料相接触， 因 此不发出声音而安静， 还有易小型化说、 高速化、 彩色化的特长， 因此近年来迅速发展。  The inkjet printing method is one of the typical color recording methods. Since the head does not come into contact with the material to be recorded, it is quiet without sound, and it is easy to be miniaturized, speeded up, and colored, and has been rapidly developed in recent years.
现有技术中， 用于喷墨打印的墨水通常通过将水溶性染料溶解于水性介质中， 并 添加可防止笔尖及喷墨喷嘴墨水阻塞的水溶性有机溶剂来制得。 这些墨水， 要求具有 高密度的打印图像、 笔尖或喷嘴不产生阻塞、 被书记录材料上的干燥性良好、 渗透少、 保存稳定性优异等性能； 另外， 所形成的图像须有耐水性、 耐光性、 耐湿性等坚牢度。  In the prior art, inks for ink jet printing are generally produced by dissolving a water-soluble dye in an aqueous medium and adding a water-soluble organic solvent which prevents clogging of the pen tip and the ink jet nozzle ink. These inks are required to have a high-density printed image, a tip or nozzle that does not block, a good drying property on a book recording material, a small penetration, and excellent storage stability. In addition, the formed image must have water resistance and light resistance. Fastness to sex, moisture resistance, etc.
随着喷墨打印技术的应用从小型打印机扩展至产业用的大型打印机， 对墨水的耐 水性、 耐湿性、 耐光性及耐气体性等有更高的标准。 对耐水性而言： 通常基质表面有 吸附多孔质氧化硅、 阳离子聚合物、 氧化铝溶胶或特殊陶瓷， 染料与这些有机或无机 的微粒及 PVA树脂等共同涂覆在纸表面， 因而可大幅度地得到改善。 对耐湿性而言： 当打印影像保存在高湿度的环境下时， 对被记录材料中染料的渗透现象具有坚牢性， 若有染料的渗透， 特别是在照片调色要求高的情况下， 会明显地降低图像品质。 对耐 光性而言： 黄、 品红、 青、 黑色的 4原色中品红色耐光性最弱， 对此的改善便成为重 要课题。  As the application of inkjet printing technology extends from small printers to large-scale printers for industrial use, there are higher standards for ink water resistance, moisture resistance, light resistance, and gas resistance. For water resistance: Usually, the surface of the substrate is adsorbed by porous silica, cationic polymer, alumina sol or special ceramic. The dye is coated on the paper surface together with these organic or inorganic particles and PVA resin. The ground is improved. For moisture resistance: When the printed image is stored in a high humidity environment, the penetration of the dye in the recorded material is fast, if there is penetration of the dye, especially in the case of high photo coloring requirements, Will significantly reduce the image quality. For light resistance: The four primary colors of yellow, magenta, cyan, and black have the weakest light resistance, and this improvement has become an important issue.
另一方面， 近年来数码照相机广泛普及， 在家庭中打印照片的机会增多， 在保存 所得的打印物时， 因市内空气中的氧化性气体而导致图像的变色也成为问题之一。 氧 化性气体是在记录纸上或在记录纸中与染料反应， 使打印的图像变色、 退色。 特别是 臭氧气体， 是促进喷墨打印图像氧化退色的主要物质， 因此， 耐臭氧气体性的改善亦 与耐光性的改善成为同样重要的课题。  On the other hand, digital cameras have become widespread in recent years, and there is an increasing chance of printing photos in the home. When the obtained printed matter is stored, discoloration of the image due to oxidizing gas in the city air is also a problem. The oxidizing gas reacts with the dye on the recording paper or in the recording paper to discolor and fade the printed image. In particular, ozone gas is a main substance for promoting oxidation and fading of ink-jet printed images. Therefore, improvement of ozone-resistant gas properties is also an important issue in improving light resistance.
喷墨墨水中所使用的品红用染料的分子骨架， 代表者是使用氧杂蒽型罗丹明染料 和由 H酸偶合而得的偶氮型染料。 然而， 罗丹明染料虽然色调及鲜艳性非常优异， 但 耐光性却极差。 而对于 H-酸类偶氮染料， 虽然颜色和耐水性较好， 但耐光性、 耐臭氧 性以及鲜艳度不足， 特别是与以铜酞菁为代表的青色染料及偶氮型黄色染料相比， 耐 光性依然不足。  The molecular skeleton of the dye for magenta used in the inkjet ink is represented by an oxazepine type rhodamine dye and an azo type dye coupled by H acid. However, the rhodamine dye is excellent in color tone and vividness, but its light resistance is extremely poor. For the H-acid azo dye, although the color and water resistance are good, the light resistance, the ozone resistance, and the vividness are insufficient, especially compared with the cyan dye and the azo yellow dye represented by copper phthalocyanine. , light resistance is still insufficient.
近年来的研究表明， 具有葸吡啶酮分子骨架的化合物是制备鲜艳、 耐光性能优异 的品红染料的优良原料， 具有鲜艳、 耐光、 耐臭氧等优点。 代表性的包括如Recent studies have shown that compounds with an indole pyridone molecular skeleton are excellent in preparation and excellent in light resistance. The excellent raw material of the magenta dye has the advantages of brightness, light resistance and ozone resistance. Representative includes
CN101370882A, CN101298526A, CN101547976A等所公开的现有技术。 The prior art disclosed in CN101370882A, CN101298526A, CN101547976A, and the like.
但现有技术中所公开的这些染料中， 尚未发现可全部满足色调、鲜明性、耐光性、 耐水性、 耐臭氧性以及溶液稳定性的染料。 再一方面， 染料在墨水中的长期稳定性与 染料的溶解度， 特别是染料在水中的溶解度有关， 而现有技术中的染料的溶解度均不 够理想， 因此， 也急需寻找溶解度更好的染料化合物。 发明内容  However, among these dyes disclosed in the prior art, dyes which can satisfy all of hue, vividness, light resistance, water resistance, ozone resistance, and solution stability have not been found. On the other hand, the long-term stability of the dye in the ink is related to the solubility of the dye, especially the solubility of the dye in water, and the solubility of the dye in the prior art is not ideal. Therefore, it is urgent to find a dye compound with better solubility. . Summary of the invention
本发明的目的在于提供一种品红用染料化合物， 该类染料应当对水的溶解性高， 具有适于喷墨打印的色彩、 鲜艳度， 并且打印图像的耐光、 耐湿、 耐臭氧坚牢性优异， 可以在喷墨记录材料上得到高鲜艳度的色调、 高强度的耐光稳定性、 高坚牢的抗臭氧 稳定性。  It is an object of the present invention to provide a dye compound for magenta which has high solubility in water, has color and vividness suitable for ink jet printing, and is resistant to light, moisture and ozone in printing images. Excellent, it can obtain high vividness hue, high intensity light stability, and high anti-ozone stability on inkjet recording materials.
本发明为解决上述问题， 经研究发现： 蒽吡啶酮 （anthrapyridone) 的磺酸化合物 可以解决上述问题。 本发明首先提供一类双核蒽吡啶酮磺酸化合物或其盐， 具有通式 I的结构：  The present invention has been made in order to solve the above problems, and it has been found that an sulfonic acid compound of anthrapyridone can solve the above problems. The present invention first provides a class of dinuclear anthrapyridone sulfonic acid compounds or salts thereof having the structure of formula I:
Figure imgf000004_0001
Figure imgf000004_0001
(I)  (I)
中：  Medium:
L是连接基团；  L is a linking group;
1^和 各自独立地选自： OH、 O(C6H5-m)(CO2H)m、 S(CH2) mSO3H、 S(CH2)mCO2H、 O(C6H5-m)(SO3H)m、 O(C10H9-m)(CO2H)m、 O(C10H9-m)(SO3H)m、 腿2、草 7)2、 SH、 SR7、 NH(C6H5-m)(CO2H)m、 NH(C6H5-m)(SO3H)m、 NH(C10H9-m)(CO2H)m、 NH(C10H9-m)(SO3H)m、 S(C6H5-m)(CO2H)m、 S(C6H5-m)(SO3H)m、 S(C10H9-m)(CO2H) S(C10H9-m)(SO3H)m ; 1^ and each independently selected from: OH, O(C 6 H 5-m )(CO 2 H) m , S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H, O(C 6 H 5-m )(SO 3 H) m , O(C 10 H 9-m )(CO 2 H) m , O(C 10 H 9-m )(SO 3 H) m , Leg 2 , Grass 7 2 , SH, SR 7 , NH(C 6 H 5-m )(CO 2 H) m , NH(C 6 H 5-m )(SO 3 H) m , NH(C 10 H 9-m )( CO 2 H) m , NH(C 10 H 9-m )(SO 3 H) m , S(C 6 H 5-m )(CO 2 H) m , S(C 6 H 5-m )(SO 3 H) m , S(C 10 H 9-m )(CO 2 H) S(C 10 H 9-m )(SO 3 H) m ;
R7是 CM垸基； R 7 is a CM group;
n是 0-2的整数；  n is an integer of 0-2;
m是 0-3的整数。  m is an integer from 0-3.
上述本发明的双核蒽吡啶酮磺酸化合物或其盐， 其中所述的！^和 R2各自独立地 选自 O(C6H5-m)(CO2H)m、 S(CH2) mSO3H、 S(CH2)mCO2H和 O(C6H5-m)(SO3H)m。 上述本发明的双核蒽吡哫酮磺酸化合物或其盐， 其中所述的 L是 -NH(CH2)pNH- -S(CH2)qS- 或化合物
Figure imgf000005_0001
The above-mentioned binuclear pyridine pyridine sulfonic acid compound of the present invention or a salt thereof, wherein said! ^ and R 2 are each independently selected from O(C 6 H 5-m )(CO 2 H) m , S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H and O(C 6 H 5-m )(SO 3 H) m . The above-mentioned dinuclear pyridone sulfonic acid compound of the present invention or a salt thereof, wherein the L is -NH(CH 2 ) p NH- -S(CH 2 ) q S- or a compound
Figure imgf000005_0001
其中： p、 q是 1-18的整数。  Where: p, q are integers from 1-18.
更为优选地， 本发明所述的双核蒽吡啶酮磺酸化合物或其盐， 是下述化合物之- (E-1至 E-10) 或其盐：  More preferably, the binuclear pyridinone sulfonic acid compound or a salt thereof according to the present invention is - (E-1 to E-10) or a salt thereof:
Figure imgf000005_0002
Figure imgf000005_0002
Figure imgf000005_0003
Figure imgf000006_0001
Figure imgf000005_0003
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000007_0001
E-9
Figure imgf000007_0002
E-9
Figure imgf000007_0002
E-10 上述本发明所述的双核蒽吡啶酮磺酸化合物或其盐， 其中所述的盐是相应双核蒽 吡啶酮磺酸化合物的锂盐、 钠盐、 钾盐、 铵盐或有机铵盐。 所述的有机铵盐阳离子具 有通式 N+R3R4R5R6结构， 其中的 R3、 、 R5、 R6各自独立地选自 11、 CM8垸基、 环 己基、 CH2CH2OH和苄基。 E-10 The above-mentioned dinuclear pyridinium sulfonate compound or a salt thereof according to the present invention, wherein the salt is a lithium salt, a sodium salt, a potassium salt, an ammonium salt or an organic ammonium salt of the corresponding dinuclear pyridone sulfonic acid compound. . The organic ammonium salt cation has a structure of the general formula N + R 3 R4R 5 R 6 wherein R 3 , R 5 , R 6 are each independently selected from the group consisting of 11, C M8 fluorenyl, cyclohexyl, CH 2 CH 2 OH and benzyl.
作为优选地， 所述双核蒽吡啶酮磺酸化合物的盐是相应双核蒽吡啶酮磺酸化合物 的锂盐、 钠盐、 钾盐、 铵盐、 单乙醇胺盐、 二乙醇胺盐、 三乙醇胺盐、 单异丙醇胺盐、 二异丙醇胺盐或三异丙醇胺盐。  Preferably, the salt of the dinuclear pyridone sulfonic acid compound is a lithium salt, a sodium salt, a potassium salt, an ammonium salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, a single of the corresponding dinuclear pyridone sulfonic acid compound. Isopropanolamine salt, diisopropanolamine salt or triisopropanolamine salt.
最为优选的， 所述的盐是相应双核蒽吡啶酮磺酸化合物的锂盐、 钠盐或铵盐。 本发明另一方面的目的在于提供上述本发明的双核蒽吡啶酮磺酸化合物或其盐的 制备方法， 包括下述步骤：  Most preferably, the salt is a lithium, sodium or ammonium salt of the corresponding dinuclear pyridone sulfonic acid compound. Another object of the present invention is to provide a process for producing the above-described dinuclear pyridinone sulfonic acid compound of the present invention or a salt thereof, comprising the steps of:
(i)式 III的化合物与苯甲酰乙酸酯按摩尔比 1:2〜5在有机溶剂中， 在 175〜180°C 条件下反应制备式 IV的化合物；  (i) a compound of the formula III and a benzoyl acetate molar ratio 1:2 to 5 in an organic solvent, reacted at 175 to 180 ° C to prepare a compound of the formula IV;
NHCOCH NHCOCH
Figure imgf000008_0001
其中所述的有机溶剂是二甲苯、 二乙苯、 三甲苯、 氯苯、 二氯苯、 硝基苯或 DMF 与 DMSO按体积比 3:1组成的混合溶剂；
Figure imgf000008_0001
The organic solvent is xylene, diethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene or a mixed solvent of DMF and DMSO in a volume ratio of 3:1;
(ii) 式 IV的化合物与发烟硫酸按摩尔比 1:50， 在 85-90 °C条件下反应 4小时制 备式 V的化合物  (ii) a compound of the formula IV is reacted with a fuming sulfuric acid molar ratio of 1:50 at a temperature of 85-90 ° C for 4 hours to prepare a compound of the formula V
Figure imgf000008_0002
Figure imgf000008_0002
(V)  (V)
(iii) 式 V的化合物与三聚氯氰按摩尔比 1 :1在阴离子乳化剂中， 用 25 %氢氧化 钠水溶液调节 PH在 3-4， 反应 3小时得制备式 VI的化合物。 (iii) A compound of the formula VI is prepared by reacting a compound of the formula V with a cyanuric chlorination ratio of 1:1 in an anionic emulsifier with a 25 % aqueous sodium hydroxide solution at a pH of 3-4 for 3 hours.
Figure imgf000008_0003
(iv)式 VI的化合物与 RH按摩尔比 1:1在 25 %氢氧化钠水溶液调整 pH，于 27-30°C 反应 1小时后， 继续在 40-45°C反应 1小时， 盐析得到式 VII的化合物。
Figure imgf000008_0003
(iv) The compound of the formula VI is adjusted to pH with a RH molar ratio of 1:1 in a 25% aqueous sodium hydroxide solution, and after reacting at 27-30 ° C for 1 hour, the reaction is further continued at 40-45 ° C for 1 hour, and salting out is obtained. A compound of formula VII.
Figure imgf000009_0001
Figure imgf000009_0001
其中， R 选自： OH、 O(C6H5-m)(CO2H)m S(CH2) mSO3H、 S(CH2)mCO2H、 O(C6H5-m)(SO3H)m、 O(C10H9-m)(CO2H)m、 O(C10H9-m)(SO3H)m、 腿2、草 7)2、 SH、 SR7、 NH(C6H5-m)(CO2H)m、 NH(C6H5-m)(SO3H)m、 NH(C10H9-m)(CO2H)m、 NH(C10H9-m)(SO3H)m、 S(C6H5-m)(CO2H)m、 S(C6H5-m)(SO3H)m、 S(C10H9-m)(CO2H) S(C10H9-m)(SO3H)m Wherein R is selected from the group consisting of: OH, O(C 6 H 5-m )(CO 2 H) m S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H, O(C 6 H 5- m )(SO 3 H) m , O(C 10 H 9-m )(CO 2 H) m , O(C 10 H 9-m )(SO 3 H) m , leg 2 , grass 7 ) 2 , SH , SR 7 , NH(C 6 H 5-m )(CO 2 H) m , NH(C 6 H 5-m )(SO 3 H) m , NH(C 10 H 9-m )(CO 2 H) m , NH(C 10 H 9-m )(SO 3 H) m , S(C 6 H 5-m )(CO 2 H) m , S(C 6 H 5-m )(SO 3 H) m , S(C 10 H 9-m )(CO 2 H) S(C 10 H 9-m )(SO 3 H) m
(v) 式 VII的化合物与 L按摩尔比 2:1在 25 %氢氧化钠水溶液调整 pH， 在 87 至 93°C反应 1小时， 后于 65±2°C下用浓盐酸调节 PH, 盐析得到式 I的化合物。  (v) Compound of formula VII is adjusted to pH with 2 molar ratio of 2:1 in 25% aqueous sodium hydroxide solution, reacted at 87 to 93 ° C for 1 hour, and then adjusted to pH with concentrated hydrochloric acid at 65 ± 2 ° C. The compound of formula I is obtained.
Figure imgf000009_0002
Figure imgf000009_0002
(I) 其中， L是 -NH( -、 -S(CH2)qS- 或化合物 L
Figure imgf000009_0003
(I) wherein L is -NH( -, -S(CH 2 ) q S- or compound L
Figure imgf000009_0003
p、 q是 1-18的整数。  p, q are integers from 1 to 18.
本发明再一方面的目的在于提供一种品红墨水组合物， 所述组合物中含有上文所 述的本发明的双核蒽吡啶酮磺酸化合物或其盐。  A further object of the present invention is to provide a magenta ink composition comprising the above-described dinuclear pyridone sulfonic acid compound of the present invention or a salt thereof.
所述的品红墨水组合物中含有水及水溶性有机溶剂。  The magenta ink composition contains water and a water-soluble organic solvent.
所述的品红墨水组合物中双核蒽吡啶酮磺酸化合物的质量百分含量为 0.1〜20%。 所述品红墨水组合物中无机杂质的质量百分含量不超过非溶剂组分总质量的 1%。 本发明另一方面的目的还在于提供上述本发明的品红墨水组合在喷墨打印中的应 用。 The mass percentage of the dinuclear pyridone sulfonic acid compound in the magenta ink composition is 0.1 to 20%. The mass percentage of inorganic impurities in the magenta ink composition does not exceed 1% of the total mass of the non-solvent component. Another object of the present invention is also to provide the use of the magenta ink combination of the present invention described above in ink jet printing.
本发明在双核蒽吡啶酮的蒽醌环上引入吸电性的水溶性基团磺酸基， 这是本领域 现有技术中不曾出现过的， 不仅可以降低分子的电子云密度， 提高抗光氧化和臭氧氧 化的能力， 而且可以提高染料的溶解度， 增强染料在墨水中的稳定性； 而将两个染料 母体连接起来， 可以提高染料图像的耐水性。 以工业溴氨酸蓝色染料为起始原料、 避 免使用现有技术中通常使用的磺酸化合物， 反应步骤少， 工艺流程短， 原料廉价， 可 本发明的式 (I)所示的化合物及其盐所制备的品红墨水组合物， 在喷墨记录纸上呈 现鲜明性、 明度极高的色调， 水溶性优异， 在墨水组合物的制造过程中， 对滤膜器的 过滤性良好。 而且， 使用该化合物的本发明的墨  The present invention introduces an electron-absorbing water-soluble group sulfonic acid group on the anthracene ring of the dinuclear pyridone, which has not appeared in the prior art in the prior art, and can not only reduce the electron cloud density of the molecule, but also improve the light resistance. Oxidation and ozone oxidation, and can improve the solubility of the dye, enhance the stability of the dye in the ink; and the two dye precursors can improve the water resistance of the dye image. The industrial bromate blue dye is used as a starting material, the sulfonic acid compound generally used in the prior art is avoided, the reaction step is small, the process flow is short, and the raw materials are inexpensive, and the compound represented by the formula (I) of the present invention and The magenta ink composition prepared from the salt exhibits a sharp color and an extremely high color tone on the ink jet recording paper, and is excellent in water solubility, and has good filterability to the filter in the production process of the ink composition. Moreover, the ink of the present invention using the compound
晶、 物理性变化、 颜色变化等， 且储藏稳定性良好。 使用本发明的含葸吡啶酮化合物 的喷墨记录用品红墨水组台物的打印物， 并不选择被记录材料 (纸、 薄膜等)而可提供 理想的品红色调， 而且本发明的品红墨水组合物可将相片色调的彩色图像色调忠实地 还原呈现， 即使打印在如相片画质用喷墨专用纸 (薄膜)的表面经无机微粒涂布的被记 求材料时， 其耐光性、 耐臭氧性、 耐湿性等的坚牢性良好， 图像的长期保存稳定。 具体实施方式 Crystal, physical changes, color changes, etc., and good storage stability. The printed matter of the red ink set of the inkjet recording article containing the anthrapyridone compound of the present invention does not select a material to be recorded (paper, film, etc.) to provide an ideal magenta tone, and the magenta of the present invention The ink composition faithfully restores the color tone of the color tone of the photo tone, and is light-resistant and resistant even when printed on a surface coated with inorganic fine particles such as inkjet paper (film) for photo quality. The fastness of ozone, moisture resistance, etc. is good, and the long-term preservation of images is stable. detailed description
本发明  this invention
Figure imgf000010_0001
Figure imgf000010_0001
(I)  (I)
通式 I中，  In the formula I,
L是连接基团， 优选 -NH(CH2)pNH -、 -S(CH2)qS- 或化合物 L
Figure imgf000010_0002
L is a linking group, preferably -NH(CH 2 ) p NH -, -S(CH 2 ) q S- or compound L
Figure imgf000010_0002
其中 p、 q是 1-18的整数， 优选 2-6的整数。  Wherein p and q are integers from 1 to 18, preferably integers from 2 to 6.
R n R2各自独立地选自： OH、 O(C6H5-m)(CO2H)m、 S(CH2) mSO3H、 S(CH2)mCO2H、 O(C6H5-m)(SO3H)m、 O(C10H9-m)(CO2H)m、 O(C10H9-m)(SO3H)m、 NH2、草 7)2、 SH、 SR7、 NH(C6H5-m)(CO2H)m、 NH(C6H5-m)(SO3H)m、 NH(C10H9-m)(CO2H)m、 NH(C10H9-m)(SO3H)m、 S(C6H5-m)(CO2H)m、 S(C6H5-m)(SO3H)m、 S(C10H9-m)(CO2H) S(C10H9-m)(SO3H)m ; R n R 2 are each independently selected from the group consisting of: OH, O(C 6 H 5-m )(CO 2 H) m , S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H, O ( C 6 H 5-m )(SO 3 H) m , O(C 10 H 9-m )(CO 2 H) m , O(C 10 H 9-m )(SO 3 H) m , NH 2 , grass 7 ) 2 , SH, SR 7 , NH(C 6 H 5-m )(CO 2 H) m , NH(C 6 H 5-m )(SO 3 H) m , NH(C 10 H 9-m )(CO 2 H) m , NH( C 10 H 9-m )(SO 3 H) m , S(C 6 H 5-m )(CO 2 H) m , S(C 6 H 5-m )(SO 3 H) m , S(C 10 H 9-m )(CO 2 H) S(C 10 H 9-m )(SO 3 H) m ;
其中， R7是 CM垸基； n是 0-2的整数； m是 0-3的整数。 Wherein R 7 is a CM fluorenyl group; n is an integer of 0-2; m is an integer of 0-3.
尤其优选的是 和 各自独立地选自 O(C6H5-m)(CO2H)m、 S(CH2) mSO3H、 S(CH2)mCO2H和 O(C6H5-m)(SO3H)m。 It is especially preferred to be independently selected from O(C 6 H 5-m )(CO 2 H) m , S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H and O(C 6 H 5-m )(SO 3 H) m .
最为优选地， 和 为相同基团， 选自： o -OC6H5(CO2H)2、 S(CH2) 3SO3H 和 p-OC6H5SO3H。 Most preferably, the sum is the same group selected from the group consisting of: o-OC 6 H 5 (CO 2 H) 2 , S(CH 2 ) 3 SO 3 H and p-OC 6 H 5 SO 3 H.
本说明书中所述及的 "垸基"均指直链或支链的垸基。  As used herein, "mercapto" refers to a straight or branched fluorenyl group.
通式 I的化合物中， 在取代的 4-氨基吡啶蒽酮的核上引入磺酸基， 增大水溶性； 进而使用连接基团 L将两个吡啶蒽酮磺酸化合物核连接， 提高耐水性。  In the compound of the formula I, a sulfonic acid group is introduced on the core of the substituted 4-aminopyridinone to increase the water solubility; and the two pyridone sulfonic acid compound cores are further connected by a linking group L to improve water resistance. .
通式 I的化合物在实际使用中， 通常以阳离子盐的形式， 所述的盐是相应双核蒽 吡啶酮磺酸化合物的锂盐、 钠盐、 钾盐、 铵盐或有机铵盐， 所述的有机铵盐阳离子具 有通式 N+R3R4R5R6结构， 其中的 R3、 、 R5、 R6各自独立地选自 11、 CM8垸基、 环 己基、 CH2CH2OH和苄基。 The compound of the formula I is in practical use, usually in the form of a cationic salt, which is a lithium salt, a sodium salt, a potassium salt, an ammonium salt or an organic ammonium salt of the corresponding dinuclear pyridone sulfonic acid compound, The organic ammonium salt cation has a structure of the general formula N + R 3 R4R 5 R 6 wherein R 3 , R 5 , R 6 are each independently selected from the group consisting of 11, C M8 fluorenyl, cyclohexyl, CH 2 CH 2 OH and benzyl. base.
更为优选的技术方案中，所述的盐是相应双核蒽吡啶酮磺酸化合物的锂盐、钠盐、 钾盐、 铵盐、 单乙醇胺盐、 二乙醇胺盐、 三乙醇胺盐、 单异丙醇胺盐、 二异丙醇胺盐 或三异丙醇胺盐。 其中以锂盐、 钠盐或铵盐最为优选。  In a more preferred embodiment, the salt is a lithium salt, a sodium salt, a potassium salt, an ammonium salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, a monoisopropanol of the corresponding dinuclear pyridone sulfonic acid compound. An amine salt, a diisopropanolamine salt or a triisopropanolamine salt. Among them, a lithium salt, a sodium salt or an ammonium salt is most preferred.
通式 I的双核蒽吡啶酮磺酸化合物的制备方法， 以单核化合物 III为基本原料， 在 有机溶剂中成环， 形成通式化合物 IV， 然后磺化并水解反应形成带氨基的通式化合物 通式 V， 然后与三聚氯氰形成中间体 VI， 再与化合物 RH反应形成通式化合物 VII， 最后以连接基 H-L-H连接形成通式化合物 I。 再经过盐的转换形成盐。  The method for preparing a dinuclear pyridinone sulfonic acid compound of the formula I, which comprises a mononuclear compound III as a basic raw material, is cyclized in an organic solvent to form a compound of the formula IV, and then sulfonated and hydrolyzed to form an amino group-containing compound. Formula V, which then forms intermediate VI with cyanuric chloride, is then reacted with compound RH to form compound of formula VII, and finally joined by a linker HLH to form compound of formula I. The salt is then converted to form a salt.
式 III的成环反应中， 蓝色蒽醌磺酸化合物 （通式 III) 与苯甲酰基乙酸酯的反应 形成化合物 IV的反应条件为：① 化合物 III与苯甲酰基乙酸酯（如甲酯、乙酯、丙酯、 异丙酯） 按照摩尔比 1 : 2〜5在有机溶剂中， 在 175〜180°C条件下反应。  In the ring-forming reaction of formula III, the reaction conditions of the reaction of the blue sulfonic acid compound (formula III) with benzoyl acetate to form compound IV are: 1 compound III and benzoyl acetate (such as a Ester, ethyl ester, propyl ester, isopropyl ester) The reaction is carried out at a molar ratio of 1: 2 to 5 in an organic solvent at 175 to 180 °C.
所述的化合物 III与苯甲酰基乙酸酯的摩尔比优选 1 :3。  The molar ratio of the compound III to the benzoyl acetate is preferably 1:3.
所述的苯甲酰基乙酸酯优选列举如甲酯、 乙酯、 丙酯、 异丙酯。  The benzoyl acetate is preferably exemplified by a methyl ester, an ethyl ester, a propyl ester or an isopropyl ester.
所述的溶剂是高沸点有机溶剂与 DMSO组成的混合溶剂，这些有机溶剂优选二甲 苯、 二乙苯、 三甲苯、 氯苯、 二氯苯、 硝基苯或 DMF。  The solvent is a mixed solvent of a high boiling organic solvent and DMSO, and these organic solvents are preferably xylene, diethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene or DMF.
式 III的成环反应优选在碱存在条件下进行， 加入反应体系的碱选自碳酸钠、碳酸 氢钠、 碳酸钾、 碳酸氢钾、 碳酸锂、 碳酸氢锂、 碳酸铵、 碳酸氢铵、 磷酸钠、 磷酸氢 二钠、 磷酸钾、 磷酸氢二钾、 磷酸铵、 磷酸氢二铵、 磷酸锂、 磷酸氢二锂、 醋酸钠、 醋酸钾、 醋酸锂、 醋酸铵、 草酸钠、 草酸钾、 草酸锂、 草酸铵、 氢氧化钠、 氢氧化钾、 氢氧化铝和氢氧化锂。 优选碳酸钠、 碳酸氢钠。 碱的加入量与化合物 III 的摩尔比为The ring-forming reaction of formula III is preferably carried out in the presence of a base selected from the group consisting of sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, lithium carbonate, lithium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate, phosphoric acid. Sodium, disodium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, ammonium phosphate, diammonium hydrogen phosphate, lithium phosphate, dilithium hydrogen phosphate, sodium acetate, Potassium acetate, lithium acetate, ammonium acetate, sodium oxalate, potassium oxalate, lithium oxalate, ammonium oxalate, sodium hydroxide, potassium hydroxide, aluminum hydroxide and lithium hydroxide. Sodium carbonate and sodium hydrogencarbonate are preferred. The molar ratio of the base added to the compound III is
1:0.1-20, 优选 1 :0.5-2.5 1:0.1-20, preferably 1:0.5-2.5
式 III的成环反应可在加压或真空的条件下提升调控反应温度，可选 0.5〜5大气压。 式 III的成环反应应当在监控下进行，使用液相色谱或薄层色谱手段控制蓝色蒽醌 染料化合物 III消失为反应终点。  The ring-forming reaction of formula III can increase the temperature of the reaction under pressure or vacuum, optionally from 0.5 to 5 atmospheres. The ring-forming reaction of formula III should be carried out under monitoring, using liquid chromatography or thin layer chromatography to control the disappearance of the blue hydrazine dye compound III as the end of the reaction.
式 III的成环反应使用分水器将生成的水和乙醇从回流冷凝器中分出，以促使反应 完成。  The ring-forming reaction of formula III uses a water separator to separate the formed water and ethanol from the reflux condenser to promote completion of the reaction.
反应结束后， 冷却， 使中间体 （通式 IV和 VI) 析出。 加入低沸点为 30〜150°C的有 机溶剂， 有利于析出完全， 可选溶剂包括甲醇、 乙醇、 丙醇、 异丙醇、 丙酮、 甲乙酮、 ***、 四氢呋喃、 二氧六环、 二氯甲垸、 氯仿、 四氯化碳、 环己垸、 石油醚、 乙酸乙 酯、 乙酸甲酯、 乙酸丁酯、 乙酸异丁酯、 乙酸仲丁酯、 甲酸乙酯、 甲酸丙酯、 甲酸丁 酯、 甲酸异丁酯、 甲酸仲丁酯。 优选甲醇、 乙醇、 丙醇、 异丙醇。  After the reaction is completed, it is cooled to precipitate an intermediate (formulas IV and VI). Adding an organic solvent with a low boiling point of 30 to 150 ° C is advantageous for precipitation. The optional solvents include methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, dioxane, and dichloroformamidine. , chloroform, carbon tetrachloride, cyclohexane, petroleum ether, ethyl acetate, methyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, ethyl formate, propyl formate, butyl formate, formic acid Isobutyl ester, sec-butyl formate. Preference is given to methanol, ethanol, propanol and isopropanol.
通式化合物 IV的磺化水解反应： 式 IV的化合物与发烟硫酸的磺化反应中， 发烟 硫酸中三氧化硫的含量 5〜15%， 优选 8〜13%， 最优 9〜12%。 反应可用相色谱或薄层色 谱手段控制反应终点。 反应结束后， 在搅拌下将磺化产物倒入冰水中， 在 40〜60°C水 解反应 0.1〜2小时。 然后加入氯化铵或氯化钠多次盐析， 冷却， 过滤， 得到式 V的化 合物。  Sulfonated hydrolysis reaction of the compound of the formula IV: In the sulfonation reaction of the compound of the formula IV with fuming sulfuric acid, the content of sulfur trioxide in the fuming sulfuric acid is 5 to 15%, preferably 8 to 13%, and most preferably 9 to 12%. . The reaction can be controlled by phase chromatography or thin layer chromatography to control the endpoint of the reaction. After completion of the reaction, the sulfonated product was poured into ice water with stirring, and the reaction was hydrolyzed at 40 to 60 ° C for 0.1 to 2 hours. Then, ammonium chloride or sodium chloride is added for multiple salting out, cooled, and filtered to obtain a compound of the formula V.
通式 I的化合物可通过常规方法成盐， 比如与氢氧化钾、 氢氧化锂、 氨水、 有机 胺反应， 即可得到相应的钾盐、 锂盐、 铵盐、 有机铵盐。 这些盐中优选锂盐、 钠盐、 钾盐、 铵盐、 单乙醇胺盐、 二乙醇胺盐、 三乙醇胺盐、 单异丙醇胺盐、 二异丙醇胺盐 或三异丙醇胺盐。 特别优选锂盐、 钠盐或铵盐。  The compound of the formula I can be salted by a conventional method, for example, by reacting with potassium hydroxide, lithium hydroxide, aqueous ammonia or an organic amine to obtain a corresponding potassium salt, lithium salt, ammonium salt or organic ammonium salt. Among these salts, lithium salts, sodium salts, potassium salts, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, diisopropanolamine salts or triisopropanolamine salts are preferred. A lithium salt, a sodium salt or an ammonium salt is particularly preferred.
本发明所述及的品红墨水组合物的优选实施方案中， 无机杂质的质量百分含量不 超过非溶剂组分总质量的 1%， 可以使用高压反渗透膜等一般方法对染料进行脱盐处 理。  In a preferred embodiment of the magenta ink composition according to the present invention, the mass percentage of the inorganic impurities does not exceed 1% of the total mass of the non-solvent component, and the dye may be desalted by a general method such as a high pressure reverse osmosis membrane. .
本发明的品红墨水组合物， 是通式 I的化合物或其盐溶解于水或水性溶剂所得的 组合物。 该组合物中， 双核蒽吡啶酮类化合物在所述墨水组合我中的含量一般 0.1〜20 % , 以 1〜15 %含量为佳， 尤其优选 2〜10%。  The magenta ink composition of the present invention is a composition obtained by dissolving a compound of the formula I or a salt thereof in water or an aqueous solvent. In the composition, the content of the dinuclear pyridone compound in the ink composition is generally 0.1 to 20%, preferably 1 to 15%, particularly preferably 2 to 10%.
本发明的品红墨水组合物中可分别含有 0〜30%的水溶性有机溶剂， 重量 0〜5 %的 墨水调制剂。 其余部分为水。  The magenta ink composition of the present invention may contain 0 to 30% of a water-soluble organic solvent and 0 to 5% by weight of an ink preparation agent, respectively. The rest is water.
本发明中所使用的水溶性有机溶剂包括： 甲醇、 乙醇、 正丙醇、 异丙醇、 正丁醇、 异丁醇、 仲丁醇、 叔丁醇等 _4垸醇； N，N-二甲基甲酰胺或 N，N-二甲基乙酰胺等羧酸 的酰胺； 2-吡咯垸酮、 N-甲基 -2-吡咯垸酮等内酰胺； 1，3-二甲基咪啉 -2-酮或 1，3-二甲 基六氢嘧啶 -2-酮等环式含氮溶剂； 丙酮、 甲基乙基酮、 2-甲基 -2-羟基戊 -4-酮等酮或酮 醇； 四氢呋喃、 二恶垸等环状醚； 乙二醇、 1，2-或 1，3-丙二醇、 1，2-或 1，4-丁二醇、 1，6- 己二醇。 二乙二醇、 三乙二醇、 四乙二醇、 二丙二醇、 硫二醇、 聚乙二醇、 聚丙二醇 等具有 C2_6亚垸基单元的单体、 低聚物或聚亚垸二醇或硫甘醇； 甘油、 己垸 -1，2，6-三 醇等多元醇（三元醇）； 乙二醇单甲醚或乙二醇单***、 二乙二醇单甲醚、 二乙二醇单 丁醚； 二乙二醇单***、三乙二醇单甲醚、三乙二醇单***等多元醇的 d_4垸基醚； γ- 丁内酯或二甲基亚砜等。 这些水溶性有机溶剂可单独或混合使用。 其中优选 2-吡咯垸 酮、 Ν-甲基 -2-吡咯垸酮、 单、 二或三乙二醇、 二丙二醇； 更佳者为 2-吡咯垸酮、 Ν- 甲基 -2-吡咯垸酮、 二乙二醇。 The water-soluble organic solvent used in the present invention includes: methanol, ethanol, n-propanol, isopropanol, n-butanol, Isobutanol, sec-butanol, tert-butanol, etc. _ 4 decyl alcohol; N, N-dimethylformamide or amide of carboxylic acid such as N,N-dimethylacetamide; 2-pyrrolidone, N- a lactam such as methyl-2-pyrrolidone; a cyclic nitrogen-containing solvent such as 1,3-dimethylmorpholin-2-one or 1,3-dimethylhexahydropyrimidin-2-one; acetone, A Ketone or keto alcohol such as ethyl ethyl ketone or 2-methyl-2-hydroxypentan-4-one; cyclic ether such as tetrahydrofuran or dioxan; ethylene glycol, 1,2- or 1,3-propanediol, 1 , 2- or 1,4-butanediol, 1,6-hexanediol. Monomers, oligomers or polyfluorenes having C 2 -6 fluorenylene units such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiol, polyethylene glycol, polypropylene glycol a diol or a thioglycol; a polyhydric alcohol (triol) such as glycerin or hexamethylene-1,2,6-triol; ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, Diethylene glycol monobutyl ether; d_ 4 mercapto ether of a polyhydric alcohol such as diethylene glycol monoethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; γ-butyrolactone or dimethyl sulfoxide Wait. These water-soluble organic solvents may be used singly or in combination. Among them, 2-pyrrolidone, fluorene-methyl-2-pyrrolidone, mono-, di- or triethylene glycol, dipropylene glycol; and more preferably 2-pyrrolidone, fluorene-methyl-2-pyrrole Ketone, diethylene glycol.
所述的墨水调制剂的具体例可列举如： 防腐防霉剂、 ρΗ调整剂、 螯合试剂、 防锈 剂、 水溶性紫外线吸收剂、 水溶性高分子化合物、 染料溶解剂、 表面活性剂等。  Specific examples of the ink preparation agent include antiseptic and antifungal agents, ρΗ adjusters, chelating agents, rust preventives, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye dissolvers, surfactants, and the like. .
防腐防霉剂的例可列举如： 有机硫磺类、 有机氮硫磺类、 有机卤素类、 卤烯丙基 砜类、 碘丙炔类、 Ν-卤垸基硫类、 腈类、 吡啶类、 8-羟基喹啉、 苯并噻唑类、 异噻唑 啉类、 二硫醇类、 吡啶氧化物类、 硝基丙垸类、 有机锡类、 酚类、 季铵盐类、 三嗪类、 噻二嗪类、 酰替苯胺类、 金刚垸类、 二硫氨基甲酸酯类、 溴化茚满酮类、 苯甲基溴乙 酸酯类、 无机盐类等化合物。 有机卤素类化合物的例可列举如： 五氯酚钠； 吡啶氧化 物类化合物的例可列举如： 2-吡啶硫醇 -1-氧化钠； 无机盐类化合物的例可列举如： 无 水醋酸钠； 异噻唑啉类化合物的例可列举如： 1，2-苯并异噻唑啉 -3-酮、 2-正辛基 -4-异 噻唑啉 -3-酮、 5-氯 -2-甲基 -4-异噻唑啉 -3-酮、 5-氯 -2-甲基 -4-异噻唑啉 -3-酮氯化镁、 5- 氯 -2-甲基 -4-异噻唑啉 -3-酮氯化钙、 2-甲基 -4-异噻唑啉 -3-酮氯化钙等。 其它的防腐防 霉剂的例可列举如： 山梨酸钠安息香酸钠等。  Examples of the antiseptic and antifungal agent include, for example, organic sulfurs, organic nitrogen sulfurs, organic halogens, haloallylsulfones, iodopropynes, anthraquinone-sulfonylsulfurs, nitriles, pyridines, and 8 -hydroxyquinoline, benzothiazoles, isothiazolines, dithiols, pyridine oxides, nitropropenes, organotins, phenols, quaternary ammonium salts, triazines, thiadiazines Compounds such as anilides, amantadines, dithiocarbamates, indanones, benzyl bromide, and inorganic salts. Examples of the organic halogen compound include, for example, sodium pentachlorophenol; examples of the pyridine oxide compound include, for example, 2-pyridinethiol-1-oxide; examples of the inorganic salt compound include, for example, anhydrous acetic acid. Examples of the isothiazoline compound include, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl 4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one Calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, and the like. Examples of other antiseptic and antifungal agents include sodium sorbate and sodium benzoate.
ρΗ调整剂并不受经调和的墨水的不良影响所波及， 只要可将墨水的 ρΗ控制 8.0 至 11.0的范围内者即可使用任意的物质。 其例可列举如： 二乙醇胺、 三乙醇胺等垸醇 胺； 氢氧化锂、 氢氧化钠、 氢氧化钾等碱金属的氢氧化物； 氢氧化铵或氨水； 或碳酸 锂、 碳酸钠、 碳酸钾等碱金属的碳酸盐。 其中以氨水为佳。  The ρΗ adjusting agent is not affected by the adverse effects of the conditioned ink, and any substance can be used as long as the ρ 墨水 of the ink can be controlled within the range of 8.0 to 11.0. Examples thereof include decylamines such as diethanolamine and triethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide or aqueous ammonia; or lithium carbonate, sodium carbonate, and potassium carbonate. An alkali metal carbonate. Among them, ammonia water is preferred.
螯合试剂的例可列举如： 乙二胺四乙酸钠、 硝基三乙酸钠、 羟基乙基乙二胺三乙 酸钠、 二乙三胺五乙酸钠、 尿咪二乙酸钠等。  Examples of the chelating agent include sodium edetate, sodium nitrotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium urethane diacetate, and the like.
防锈剂的例可列举如： 酸性亚硫酸盐、 硫代硫酸钠、 巯基乙酸铵、 亚硝酸二异丙 基铵、 季戊四醇四硝酸酯、 亚硝酸二环己铵等。 水溶性紫外线吸收剂的例可列举如： 经磺化的二苯甲酮或经磺化的苯并***等。 水溶性高分于化合物的例可列举如： 聚乙烯醇、 纤维素衍生物、 多胺、 多亚胺等。 染料溶解剂的例可列举如： 尿素、 ε-己内酰胺、 碳酸二乙酯等。 Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and the like. Examples of the water-soluble ultraviolet absorber include, for example, a sulfonated benzophenone or a sulfonated benzotriazole. Examples of the water-soluble high-concentration compound include polyvinyl alcohol, a cellulose derivative, a polyamine, a polyimine, and the like. Examples of the dye solubilizing agent include urea, ε-caprolactam, diethyl carbonate and the like.
表面活性剂的例可列举如： 阴离子型表面活性剂、 两性表面活性剂、 阳离子型表 面活性剂、 非离子型表面活性剂等。 阴离子型表面活性剂的例可列举如： 垸基磺基羧 酸盐、 α-烯烃磺酸盐、 聚氧亚乙基垸基醚乙酸盐、 Ν-酰基氨基酸及其盐。 Ν-酰基甲基 牛磺酸盐、 香茅酸皂、 蓖麻油硫酸酯盐、 月桂基醇硫酸酯盐、 垸基酚型磷酸酯、 垸基 型磷酸酯、 垸基烯丙基磺酸盐、 二乙基磺基琥珀酸盐、 二乙基己基磺基琥珀酸、 二辛 基磺基琥珀酸盐等。 阳离子型表面活性剂的例可列举如： 2-乙烯基吡啶衍生物、 聚 4- 乙烯基吡啶衍生物等。 两性型表面活性剂的例可列举如： 月桂基二甲基氨基乙酸甜菜 碱、 2-垸基 -Ν-羧甲基 -Ν-羟基乙基咪唑啉鑰甜菜碱、 椰子油脂肪酰胺丙基二甲基氨基 乙酸甜菜碱、 聚辛基聚氨基乙基甘氨酸的其它咪唑啉衍生物等。 非离子型表面活性剂 的例可列举如： 聚氧乙烯基壬基苯基醚、 聚氧乙烯基辛基苯基醚、 聚氧乙烯基月桂基 苯基醚、 聚氧乙烯基辛基苯基醚、 聚氧乙烯基油基醚、 聚氧乙烯基月桂基醚、 聚氧乙 烯基垸基醚等醚类； 聚氧乙烯基油酸、 聚氧乙烯基油酸酯、 聚氧乙烯基二硬脂酸酯、 山梨糖醇酐月桂酸酯、 山梨糖醇酐单硬脂酸酯、 山梨糖醇酐单油酸酯、 山梨糖醇酐倍 半油酸酯、 聚氧乙烯基单油酸酯、 聚氧乙烯基硬脂酸酯等酯类； 2，4，7，9-四甲基 -5-癸炔 — 4，7-二醇、 3，6-二甲基 -4-辛炔 -3，6-二醇、 3，5-二甲基 -1-己炔 -二醇等垸炔二醇类 （例如： 日信化学公司制造的 Surfynol 104, 82、 465、 Olfme STG等) 等。 这些的墨水调制剂 可单独或混合使用。  Examples of the surfactant include anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants. Examples of the anionic surfactant include, for example, a mercaptosulfocarboxylate, an α-olefinsulfonate, a polyoxyethyleneetherether acetate, a hydrazinoylamino acid, and a salt thereof. Ν-acylmethyltaurate, citronellyl soap, castor oil sulfate, lauryl sulfate, nonylphenol phosphate, thiol phosphate, decyl propyl sulfonate, Diethyl sulfosuccinate, diethylhexyl sulfosuccinic acid, dioctyl sulfosuccinate, and the like. Examples of the cationic surfactant include a 2-vinylpyridine derivative and a poly-4-vinylpyridine derivative. Examples of the amphoteric surfactant include, for example, lauryl dimethylaminoacetic acid betaine, 2-mercapto-indenyl-carboxymethyl-hydrazine-hydroxyethylimidazoline-betaine, and coconut oil fatty acid amide propyl Methylaminoacetic acid betaine, other imidazoline derivatives of polyoctyl polyaminoethylglycine, and the like. Examples of the nonionic surfactant include, for example, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene octylphenyl group. Ethers such as ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene decyl ether; polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene urethane Fatty acid ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, Esters such as polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3 a decynediol such as 6-diol or 3,5-dimethyl-1-hexyne-diol (for example, Surfynol 104, 82, 465, Olfme STG, etc., manufactured by Nisshin Chemical Co., Ltd.). These ink modulating agents can be used singly or in combination.
本发明的墨水组合物是将通式 I的化合物或其盐溶于水或上述水性溶剂中， 可依 需要使与上述墨水调制剂等一起溶解而制造。  In the ink composition of the present invention, the compound of the formula I or a salt thereof is dissolved in water or the above aqueous solvent, and if necessary, it can be produced by dissolving together with the above-mentioned ink preparation agent or the like.
在上述制造方法中， 对各成分的溶解顺序并无特别限制。 可预先使染料溶解于水 或上述水性溶剂中， 添加墨水调制剂使的溶解， 亦可在将染料溶解于水后添加水性溶 剂、 墨水调制剂使之溶解。 亦可与此的顺序不同。 更可在将含该染料的反应液或含该 色素的溶解液反渗透膜进行脱盐处理的溶液中， 添加水性溶剂、 墨水调制剂而制造墨 水组合物。 在调制墨水组合物时， 所使用的水宜为离子交换水或蒸熘水等杂质较少的 去离子水。 然后使用滤膜过滤器等进行精密过滤并去除夹杂物。 进行精密过滤的滤膜 孔径通常为 1微米至 0.1微米， 优选 0.8微米至 0.2微米。  In the above production method, the order of dissolution of each component is not particularly limited. The dye may be dissolved in water or the above aqueous solvent in advance, and dissolved by adding an ink preparation agent. After the dye is dissolved in water, an aqueous solvent or an ink preparation agent may be added to dissolve the dye. It can also be different from this order. Further, an aqueous ink or an ink preparation agent may be added to a solution obtained by subjecting the reaction liquid containing the dye or the solution containing the dye to a desalting treatment to prepare an ink composition. When the ink composition is prepared, the water to be used is preferably ion-exchanged water or deionized water having less impurities such as distilled water. Then, a filter or the like is used for precision filtration and removal of inclusions. The pore size of the filter for precision filtration is usually from 1 μm to 0.1 μm, preferably from 0.8 μm to 0.2 μm.
本发明的水溶性双核吡啶蒽酮磺酸化合物的品红墨水组合物适于使用在盖印、 复 印、 标记、 笔记、 制图、 盖章或打印， 特别是用于喷墨打印。 其优点是所得图像对于 水、 日光、 臭氧以及摩擦具有优良耐性， 也可以被用来拼色， 特别是组成黑色。 The magenta ink composition of the water-soluble dinuclear pyridone sulfonic acid compound of the present invention is suitable for use in stamping, copying, marking, taking, drawing, stamping or printing, particularly for ink jet printing. The advantage is that the resulting image is Water, sunlight, ozone and friction have excellent resistance and can also be used for color matching, especially for black.
本发明的着色体是以上述本发明的通式 I的化合物或其盐所示的染料， 可用于许 多基质着色， 如： 纸、 纤维或布 （纤维素、 尼龙、 羊毛等）、 皮革、 滤色器用基材等， 但不限于此。 着色方法可列举如： 浸染法、 印染法、 网版印刷等印刷法、 喷墨打印等 方法， 而以喷墨打印法为佳。  The coloring matter of the present invention is a dye represented by the above compound of the formula I of the present invention or a salt thereof, and can be used for coloring a plurality of substrates, such as: paper, fiber or cloth (cellulose, nylon, wool, etc.), leather, filter. The substrate for a color filter or the like is not limited thereto. The coloring method may be, for example, a method such as a dip dyeing method, a printing method, a screen printing method, or the like, or an ink jet printing method, and an ink jet printing method is preferred.
可适用本发明的喷墨打印方法的被记录基材的可列举如： 纸、 薄膜等信息传递用 薄片、 纤维以及皮革等。 在信息传递用薄片方面， 通常需经表面处理， 这些基材中设 置墨水吸收层。 墨水吸收层是例如将阳离子等聚合物经浸渍或涂布于上述基材， 涂层 中还含多孔质二氧化硅、 氧化铝溶胶或特殊陶瓷等， 这些白色无机物与聚乙烯醇或聚 乙烯吡咯垸酮等亲水性聚合物共同经由涂布于上述基材表面。 设有这些墨水吸附层的 薄片一般称为喷墨专用纸 /薄膜或光泽纸 /薄膜，例如有：专业用光面纸、顶级用光面纸、 垫光面纸 （佳能制造）、 照片用纸光泽、 光垫纸、 超细专用光泽薄膜 （爱普生制造）、 优质增光用纸、优质光泽薄膜、光用纸（惠普制造）、等。 另外， 当然亦可利用普通纸。  Examples of the substrate to be recorded which can be applied to the ink jet printing method of the present invention include sheets for information transmission such as paper and film, fibers, leather, and the like. In the case of sheets for information transfer, surface treatment is usually required, and an ink absorbing layer is provided in these substrates. The ink absorbing layer is, for example, a polymer such as a cation which is impregnated or coated on the substrate, and the coating layer further contains porous silica, alumina sol or special ceramics, etc., and these white inorganic substances are polyvinyl alcohol or polyethylene. A hydrophilic polymer such as pyrrolidone is applied together to the surface of the substrate. Sheets provided with these ink absorbing layers are generally referred to as inkjet papers/films or glossy papers/films, such as: professional glossy paper, top gloss paper, mat gloss paper (made by Canon), photo paper. Gloss, mat paper, ultra-thin special glossy film (made by Epson), high-quality glossing paper, high-quality glossy film, glossy paper (made by HP), etc. In addition, plain paper can of course be used.
通常， 在上述表面涂有多孔性白色无机物的基质上打印图像， 由臭氧所引起的退 变色变大， 但由于本发明的水性品红色墨水组合物的耐气体性优异， 因此对此类基材 的打印可发挥特别的效果。  Usually, an image is printed on a substrate coated with a porous white inorganic substance, and the discoloration caused by ozone is increased. However, since the aqueous magenta ink composition of the present invention is excellent in gas resistance, such a base is The printing of the material can have a special effect.
多孔性白色无机物的例如： 碳酸钙、 高岭土、 滑石、 黏土、 硅藻土、 合成非晶质 二氧化硅、 硅酸铝、 硅酸镁、 硅酸钙。 氢氧化铝、 氧化铝、 锌钡石、 沸石、 硫酸钡、 硫酸钙、 二氧化钛、 硫化锌、 碳酸锌等。  Examples of the porous white inorganic substance include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, and calcium silicate. Aluminum hydroxide, aluminum oxide, ettringite, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinc carbonate, and the like.
在本发明的喷墨打印中， 除了常用的黄色、 青色墨水组合物以外， 另有绿色墨水 组合物、 橙色墨水组合物、 蓝色（或紫色）墨水组合物以及本发明的品红色墨水组合， 必要时亦可并用黑色墨水组合物等。 各色的墨水组合物经注入各自的墨盒， 分别装在 喷墨打印机的既定位置而使用。 喷墨打印机的例可列举如： 利用压电方式的打印机或 利用经加热产生泡的发泡方式的打印机等。  In the inkjet printing of the present invention, in addition to the usual yellow, cyan ink composition, there are also a green ink composition, an orange ink composition, a blue (or purple) ink composition, and a magenta ink combination of the present invention. A black ink composition or the like may be used in combination as necessary. The ink compositions of the respective colors are injected into respective ink cartridges and used in a predetermined position of the ink jet printer. Examples of the ink jet printer include a piezoelectric printer or a foaming printer that generates bubbles by heating.
本发明的水性品红色墨水组合物为鲜明的品红色， 尤其在喷墨光泽纸中具有高鲜 明的色调， 记录图像的坚牢度亦高， 亦对人体的安全性高。  The water-based magenta ink composition of the present invention is a vivid magenta color, and particularly has a high vivid color tone in ink-jet glossy paper, and the recorded image has high fastness and high safety to the human body.
本发明的墨水组合物在贮藏中不会发生沉淀或分离。 而且， 于喷墨打印中使用本 发明的墨水时， 亦不会阻塞喷头。 本发明的墨水即使由连续式喷墨打印机在固定较长 时间、 或断断续续地使用条件下， 皆不发生物理性质的变化。  The ink composition of the present invention does not precipitate or separate during storage. Moreover, when the ink of the present invention is used in ink jet printing, the head is not blocked. The ink of the present invention does not undergo physical property changes even if it is used by a continuous ink jet printer for a long period of time or intermittent use.
如无特殊说明， 本说明书中的份、 百分含量分别是指质量份和质量百分含量。 下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明， 但不以 任何方式限制本发明。 实施例 1.制备化合物 E-1 Unless otherwise stated, the parts and percentages in this specification refer to the parts by mass and mass percentage, respectively. The following non-limiting examples may enable those of ordinary skill in the art to more fully understand the present invention, but not The invention is limited in any way. Example 1. Preparation of Compound E-1
( 1 ) 在 210份邻二氯苯中， 加入 60份二甲基甲亚砜， 搅拌下依次加入 142.2份 C.I. 酸性蓝 324 (钠盐）、 3.6份碳酸钠、 135.0份苯甲酰基乙酸乙酯并升温。 在 175至 180°C的 温度反应 6小时， 反应中所生成的乙醇及水经共沸蒸熘被蒸出反应***外，颜色逐步由 蓝色变为紫色， 液相色谱仪检测反应完成 （约需要 6小时）。 冷却， 在 30°C添加 300份 异丙醇并搅拌 30分钟后，过滤分离出固体，并将所得的滤饼以 400份异丙醇清洗、干燥， 得到 155份淡紫色结晶 E1-1 (以游离磺酸表示， 钠盐）。 在水中最大吸收 535和 560 nm， 质谱 (EI-MS)m/z(-): 578.1 ([M-H]_1)。 中间体染料 El-1 (以游离磺酸 SO3H计） 最丰精 (1) In 210 parts of o-dichlorobenzene, 60 parts of dimethyl sulfoxide was added, and 142.2 parts of CI Acid Blue 324 (sodium salt), 3.6 parts of sodium carbonate, and 135.0 parts of ethyl benzoylacetate were sequentially added with stirring. And warming up. After reacting at a temperature of 175 to 180 ° C for 6 hours, the ethanol and water formed in the reaction are distilled out of the reaction system by azeotropic distillation, and the color gradually changes from blue to purple, and the reaction is completed by a liquid chromatograph. It takes 6 hours). After cooling, 300 parts of isopropanol was added at 30 ° C and stirred for 30 minutes, and the solid was separated by filtration, and the obtained cake was washed with 400 parts of isopropyl alcohol and dried to obtain 155 parts of lavender crystal E1-1 ( Free sulfonic acid means sodium salt). Maximum absorption in water 535 and 560 nm, mass spectrometry (EI-MS) m/z (-) : 578.1 ([MH] _1 ). Intermediate dye El-1 (based on free sulfonic acid SO 3 H)
Figure imgf000016_0001
Figure imgf000016_0001
(2) 在 300份 95.0%硫酸中， 搅拌和冷却下， 慢慢添加 270.0份 50.0%发烟硫酸， 调 制 570份 12%发烟硫酸。 在水冷下所得的发烟硫酸中， 在 50°C添加 96份上述中间染料 E1-1并升温。 在 85至 90°C中进行 4小时的磺化反应。 然后冷却， 在搅拌下将反应液缓慢 倒入 720份冰水中， 维持液温在 50°C以下。添加水使液量成为 960份， 过滤除去不溶物。 再加入冰使液总量为 1200份，温度维持在 60-65°C，再加 120份氯化钠并保温搅拌 2小时， 产物晶体析出， 过滤分离。 将所得的结晶以 500份 20%氯化钠水溶液清洗并充分压干， 得到含 133.2份初产物湿饼。湿滤饼溶于 600份水中，加入氯化钠 90份，然后搅拌 2小时， 过滤得到红色染料的晶体， 干燥得红色染料的晶体 E1-NH2染料 93份。 在水中最大吸收 波长 545nm。质谱 (EI-MS)m/z(-): 258·1([Μ-3Η]3- /3)、 387.5([Μ-2Η]2" /2), 776.0([Μ-Η]"1)ο 染料 （以游离磺酸计） 最丰精确分子质量数 Μ为 777.0。 (2) In 300 parts of 95.0% sulfuric acid, 270.0 parts of 50.0% fuming sulfuric acid was slowly added under stirring and cooling to prepare 570 parts of 12% fuming sulfuric acid. In the fuming sulfuric acid obtained under water cooling, 96 parts of the above intermediate dye E1-1 was added at 50 ° C and the temperature was raised. The sulfonation reaction was carried out at 85 to 90 ° C for 4 hours. After cooling, the reaction solution was slowly poured into 720 parts of ice water with stirring to maintain the liquid temperature below 50 °C. Water was added to make the amount of the liquid 960 parts, and the insoluble matter was removed by filtration. Further, ice was added to make the total amount of the liquid 1200 parts, the temperature was maintained at 60-65 ° C, 120 parts of sodium chloride was further added and the mixture was kept under stirring for 2 hours, and the product crystals were precipitated and separated by filtration. The obtained crystal was washed with 500 parts of a 20% aqueous sodium chloride solution and sufficiently dried to obtain 133.2 parts of a preliminary product wet cake. The wet cake was dissolved in 600 parts of water, and 90 parts of sodium chloride was added thereto, followed by stirring for 2 hours, and the crystals of the red dye were obtained by filtration, and dried to obtain 93 parts of a crystal of the red dye D1-NH 2 dye. The maximum absorption wavelength in water is 545 nm. Mass Spectrometry (EI-MS) m/z(-) : 258·1([Μ-3Η] 3 - /3), 387.5([Μ-2Η] 2 " /2), 776.0([Μ-Η]" 1 ) o dye (the free acid basis) of the most abundant precise molecular mass Μ number of 777.0.
Figure imgf000016_0002
(3 ) 在 60份水中， 添加 67.7份上述染料 E1-NH2化合物的湿饼， 然后加入 25%氢氧 化钠 （约 24份） 并搅拌， 调节 pH 3至 4， 使体系溶解。 另夕卜， 在 60份的冰水中滴入 0.4 份阴离子乳化剂溶解， 加入 8.9份三聚氯氰， 搅拌 30分钟， 所得的悬浮液中加入到上述 E1-NH2的化合物溶液中， 同时滴入 10%NaOH水溶液， 使 pH维持在 2.7至 3，在 25至 30°C 下进行 3小时， 得到一次缩合反应中间产物 E1-C12 (以游离酸性形式表示） 的反应液。 在水中最大吸收波长 520nm。 质谱 (EI-MS)m/z (-)： 230.0、 230.5([M-4H]474), 235.5和 236.0 ([M-5H+Na]474), 241.0、 241.5 ([M-6H+2Na]474), 321.6、 322.3 ([M-5H+2Na]373, 329.0、 329.6 ([M-6H+3Na]373， 505.0、 506.0 ([M-6H+4Na]272。 染料 （以游离磺酸计） 最丰精确分子质量数 M为 923.9和 925.9。
Figure imgf000016_0002
(3) In 60 parts of water, 67.7 parts of a wet cake of the above dye E1-NH 2 compound was added, followed by addition of 25% sodium hydroxide (about 24 parts) and stirred to adjust the pH 3 to 4 to dissolve the system. In addition, 0.4 parts of an anionic emulsifier was added dropwise to 60 parts of ice water, 8.9 parts of cyanuric chloride was added, and the mixture was stirred for 30 minutes, and the resulting suspension was added to the above-mentioned compound solution of E1-NH 2 while dropping. A 10% aqueous NaOH solution was added to maintain the pH at 2.7 to 3, and it was carried out at 25 to 30 ° C for 3 hours to obtain a reaction liquid of a condensation reaction intermediate E1-C1 2 (expressed in a free acidic form). The maximum absorption wavelength in water is 520 nm. Mass Spectrum (EI-MS) m/z (-): 230.0, 230.5 ([M-4H] 4 74), 235.5 and 236.0 ([M-5H+Na] 4 74), 241.0, 241.5 ([M-6H+ 2Na] 4 74), 321.6, 322.3 ([M-5H+2Na] 3 73, 329.0, 329.6 ([M-6H+3Na] 3 73, 505.0, 506.0 ([M-6H+4Na] 2 72. Dyes ( The most abundant molecular mass M is 923.9 and 925.9 in terms of free sulfonic acid.
Figure imgf000017_0001
Figure imgf000017_0001
(4) 在含有上述 E1-C12的反应液中， 加冰使温度调整至 5°C。 滴入 25 %氢氧化钠水 溶液调整 pH为 5-6。 另外， 在 40份的水中加入 15.4份 5-羟基间苯二甲酸钠以及 25%氢氧 化钠水溶液， 调节 pH为 9， 形成水溶液。 在上述 5°C的反应液中， 于 30分钟内滴入该 5- 羟基间苯二甲酸酯水溶液。 不断加入冰和氢氧化钠水溶液， pH值维持在 9.0±0.3， 升温 到 27-30°C， 在该温度下及 pH值下反应 1小时， 然后在 40-45°C反应 1小时。 反应结束后， 加水使液量调整至约 350份的后， 过滤去除不溶物。 然后加入水使液量调整至 400份， 将温度维持在 65±2°C， 加入浓盐酸使 pH值调整至 3， 然后在 15分钟内加入 40份的食盐， 再搅拌 1小时， 产物盐析出来， 过滤， 并用 150份 20 %氯化钠水溶液洗涤， 得到以式 El-ArCl所示化合物 （以游离磺酸形式表示， 钠盐） 的红色湿饼。 将上述湿饼加入 lOOOmL水中， 用高压反渗透膜脱除无机盐， 得到无盐染料溶液， 其最大吸收波长为 529nm (水溶液中）。 质谱 （EI-MS) m/z (-)： 213.0([M-5H]5" /5), 266.5([M-4H]4" /4), 355.7([M-3Hf /3)、 534.0([M-2Hf /2)。 染料 El-A!-Cl (以游离磺酸计） 最丰精确分子 质量数 M为 1070.0。
Figure imgf000018_0001
(4) In the reaction liquid containing the above E1-C1 2 , ice was added to adjust the temperature to 5 °C. The pH was adjusted to 5-6 by dropwise addition of a 25% aqueous sodium hydroxide solution. Further, 15.4 parts of sodium 5-hydroxyisophthalate and a 25% aqueous sodium hydroxide solution were added to 40 parts of water to adjust the pH to 9, thereby forming an aqueous solution. The 5-hydroxyisophthalate aqueous solution was added dropwise to the reaction solution at 5 ° C for 30 minutes. The ice and aqueous sodium hydroxide solution were continuously added, the pH was maintained at 9.0 ± 0.3, and the temperature was raised to 27 to 30 ° C, and the reaction was carried out at this temperature and pH for 1 hour, and then at 40 to 45 ° C for 1 hour. After the completion of the reaction, water was added to adjust the amount of the liquid to about 350 parts, and the insoluble matter was removed by filtration. Then add water to adjust the liquid amount to 400 parts, maintain the temperature at 65 ± 2 ° C, add concentrated hydrochloric acid to adjust the pH to 3, then add 40 parts of salt in 15 minutes, stir for another hour, the product salting out It was filtered, washed with 150 parts of a 20% aqueous sodium chloride solution to give a red wet cake of the compound (formed as the free sulfonic acid, sodium salt) of the compound of the formula El-A r Cl. The wet cake was added to 1000 mL of water, and the inorganic salt was removed by a high pressure reverse osmosis membrane to obtain a salt-free dye solution having a maximum absorption wavelength of 529 nm (in an aqueous solution). Mass Spectrometry (EI-MS) m/z (-): 213.0 ([M-5H] 5 " /5), 266.5 ([M-4H] 4 " /4), 355.7 ([M-3Hf /3), 534.0 ([M-2Hf /2). The dye El-A!-Cl (based on free sulfonic acid) has the most accurate molecular mass number M of 1070.0.
Figure imgf000018_0001
E1 -A1 -CI  E1 -A1 -CI
(5 ) 在含有上述 El-ArCl所示化合物的反应液中， 加入 1.2份乙二胺， 搅拌， 滴入 25 %苛性钠水溶液将 pH值维持在 8.7至 9.3， 并在 87至 93 °C的温度下使反应 1 小时。反应后，添加水使液量调整至约 400份后，经过滤去除不溶解物。升温到 65±2°C， 滴入浓盐酸使 pH值调整至 3。 接着， 在 15分钟内加入 40份的食盐， 搅拌 1小时， 过 滤所析出的结晶， 用 150份 20%食盐水溶液清洗， 得到以下述式 E1所示化合物 （以 游离磺酸形式表示， 钠盐） 的红色湿滤饼。 将所得湿滤饼加入 700 份甲醇中， 在 60 至 65°C中加热、 搅拌并维持 1小时后过滤结晶， 以甲醇清洗、 干燥， 得到 35.1份 E1 纯染料红色结晶。 水溶液中最大吸收波长： 510、 529nm。 质谱 (EI-MS)m/z(-): 424.6 ([M-5H]575), 429.0 ([M-6H+Na]575), 531.0 ([M-4H]474), 536.5 ([M-5H+Na]474), 542.0 ([M-6H+2Na]474), 723.0 ([M-5H+2Na]373, 686.3 ([M-6H+3Na]373, 1107.0 ([M-6H+4Na]272。 染料 （以游离磺酸计） 最丰精确分子质量数 为 2128.0。 (5) In the reaction solution containing the compound represented by the above El-A r Cl, 1.2 parts of ethylenediamine is added, stirred, and a 25% aqueous solution of caustic soda is added dropwise to maintain the pH at 8.7 to 9.3, and at 87 to 93 °. The reaction was allowed to proceed for 1 hour at a temperature of C. After the reaction, water was added to adjust the amount of the liquid to about 400 parts, and the insoluble matter was removed by filtration. The temperature was raised to 65 ± 2 ° C, and concentrated hydrochloric acid was added dropwise to adjust the pH to 3. Next, 40 parts of salt was added over 15 minutes, and the mixture was stirred for 1 hour, and the precipitated crystal was filtered, and washed with 150 parts of a 20% aqueous salt solution to obtain a compound represented by the following formula E1 (in the form of a free sulfonic acid, sodium salt). Red wet filter cake. The obtained wet cake was added to 700 parts of methanol, heated at 60 to 65 ° C, stirred for 1 hour, and then filtered, washed with methanol, and dried to give 35.1 parts of E1 pure dye red crystals. Maximum absorption wavelength in aqueous solution: 510, 529 nm. Mass Spectrum (EI-MS) m/z (-) : 424.6 ([M-5H] 5 75), 429.0 ([M-6H+Na] 5 75), 531.0 ([M-4H] 4 74), 536.5 ( [M-5H+Na] 4 74), 542.0 ([M-6H+2Na] 4 74), 723.0 ([M-5H+2Na] 3 73, 686.3 ([M-6H+3Na] 3 73, 1107.0 ( [M-6H+4Na] 2 72. Dye (based on free sulfonic acid) The most accurate molecular mass is 2128.0.
Figure imgf000018_0002
实施例 2.制备化合物 E-2
Figure imgf000018_0002
Example 2. Preparation of Compound E-2
按实施例 1中的步骤 （1 ) - (3 ) 制备出化合物 E1-C12 Compound E1-C1 2 was prepared according to the steps (1) - (3) in Example 1.
(4) 在含有上述 E1-C12的反应液中， 加冰使温度调整至 5°C。 滴入 25 %氢氧化钠 水溶液调整 pH为 5-6。 另夕卜， 在 40份的水中加入 13.4份对羟基苯磺酸钠以及 25%氢 氧化钠水溶液， 调节 pH为 9， 形成水溶液。 在上述 5°C的反应液中， 于 30分钟内滴 入该对羟基苯磺酸钠水溶液。 不断加入冰和氢氧化钠水溶液， pH值维持在 9.0±0.3， 升温到 27-30°C， 在该温度下及 pH值下反应 1小时， 然后在 40-45°C反应 1小时。 反 应结束后， 加水使液量调整至约 350份的后， 过滤去除不溶物。 然后加入水使液量调 整至 400份， 将温度维持在 65±2°C， 加入浓盐酸使 pH值调整至 3， 然后在 15分钟内 加入 40份的食盐， 再搅拌 1小时， 产物盐析出来， 过滤， 并用 150份 20%氯化钠水 溶液洗涤， 得到以式 ES-ArCl所示化合物（以游离磺酸形式表示， 钠盐）的红色湿饼。 将上述湿饼加入 lOOOmL水中， 用高压反渗透膜脱除无机盐， 得到无盐染料溶液， 其 最大吸收波长为 528n (4) In the reaction liquid containing the above E1-C1 2 , ice was added to adjust the temperature to 5 °C. The pH was adjusted to 5-6 by dropwise addition of a 25% aqueous sodium hydroxide solution. Further, 13.4 parts of sodium p-hydroxybenzenesulfonate and 25% aqueous sodium hydroxide solution were added to 40 parts of water to adjust the pH to 9, and an aqueous solution was formed. In the above reaction liquid at 5 ° C, the aqueous sodium p-hydroxybenzenesulfonate solution was added dropwise over 30 minutes. The ice and aqueous sodium hydroxide solution were continuously added, the pH was maintained at 9.0 ± 0.3, and the temperature was raised to 27 to 30 ° C, and the reaction was carried out at this temperature and pH for 1 hour, and then at 40 to 45 ° C for 1 hour. Counter After completion, water was added to adjust the liquid amount to about 350 parts, and the insoluble matter was removed by filtration. Then add water to adjust the liquid amount to 400 parts, maintain the temperature at 65 ± 2 ° C, add concentrated hydrochloric acid to adjust the pH to 3, then add 40 parts of salt in 15 minutes, stir for another hour, the product salting out It was filtered, washed with 150 parts of a 20% aqueous sodium chloride solution to give a red wet cake of the compound of the formula ES-ArCl (in the form of the free sulfonic acid, sodium salt). The wet cake is added to 1000 mL of water, and the inorganic salt is removed by a high pressure reverse osmosis membrane to obtain a salt-free dye solution having a maximum absorption wavelength of 528 n.
Figure imgf000019_0001
Figure imgf000019_0001
(5 ) 在含有上述 E2-ArCl所示化合物的反应液中， 加入 1.2份乙二胺， 搅拌， 滴入 25 %苛性钠水溶液将 pH值维持在 8.7至 9.3， 并在 87至 93 °C的温度下使反应 1 小时。反应后，添加水使液量调整至约 400份后，经过滤去除不溶解物。升温到 65±2°C， 滴入浓盐酸使 pH值调整至 3。 接着， 在 15分钟内加入 40份的食盐， 搅拌 1小时， 过 滤所析出的结晶， 用 150份 20%食盐水溶液清洗， 得到以下述式 E2所示化合物 （以 游离磺酸形式表示， 钠盐） 的红色湿滤饼。 将所得湿滤饼加入 700 份甲醇中， 在 60 至 65°C中加热、 搅拌并维持 1小时后过滤结晶， 以甲醇清洗、 干燥， 得到 35.1份 E2 纯染料红色结晶。 水溶液中最大吸收波长： 510、 528nm。(5) In the reaction solution containing the compound represented by the above E2-A r Cl, 1.2 parts of ethylenediamine is added, stirred, and a 25% aqueous solution of caustic soda is added dropwise to maintain the pH at 8.7 to 9.3, and at 87 to 93 °. The reaction was allowed to proceed for 1 hour at a temperature of C. After the reaction, water was added to adjust the amount of the liquid to about 400 parts, and the insoluble matter was removed by filtration. The temperature was raised to 65 ± 2 ° C, and concentrated hydrochloric acid was added dropwise to adjust the pH to 3. Next, 40 parts of salt was added over 15 minutes, and the mixture was stirred for 1 hour, and the precipitated crystals were filtered and washed with 150 parts of a 20% aqueous salt solution to obtain a compound represented by the following formula E2 (in the form of a free sulfonic acid, sodium salt). Red wet filter cake. The obtained wet cake was added to 700 parts of methanol, heated at 60 to 65 ° C, stirred for 1 hour, and then filtered, washed with methanol and dried to give 35.1 parts of E2 pure dye red crystals. Maximum absorption wavelength in aqueous solution: 510, 528 nm.
Figure imgf000019_0002
采用类似方法制备化合物 E-4、 E-5、 E-6、 E-8、 E-9、 E-10:
Figure imgf000019_0002
Compounds E-4, E-5, E-6, E-8, E-9, E-10 were prepared in a similar manner:
将实施例 1步骤（4)中的 5-羟基间苯二甲酸钠换成巯基丙磺酸钠， 可制备出化合 物 E-3  The compound E-3 can be prepared by replacing sodium 5-hydroxyisophthalate in the step (4) of the first embodiment with sodium mercaptopropanesulfonate.
将实施例 1步骤 （5 ) 中的乙二胺换成乙二硫醇， 可制备出化合物 E-7  Compound E-7 can be prepared by replacing ethylenediamine in step (5) of Example 1 with ethanedithiol.
将实施例 1步骤 （5 ) 中的乙二胺换成化合物 L 可制备出化合物 E-4  Compound E-4 can be prepared by replacing ethylenediamine in step (5) of Example 1 with compound L.
将实施例 2步骤 （5 ) 中的乙二胺换成化合物 L 可制备出化合物 E-5 将实施例 1 步骤 （4) 中的 5-羟基间苯二甲酸钠换成巯基丙磺酸钠、 步骤 （5 ) 中 的乙二胺换成化合物 L 可制备出化合物 E-6。 Compound E-5 can be prepared by replacing ethylenediamine in step (5) of Example 2 with compound L. Compound E-6 can be prepared by replacing sodium 5-hydroxyisophthalate in step (4) with sodium decyl propane sulfonate and ethylenediamine in step (5) with compound L.
将实施例 2步骤 （5 ) 中的乙二胺换成乙二硫醇， 可制备出化合物 E-8  Compound E-8 can be prepared by replacing ethylenediamine in step (5) of Example 2 with ethanedithiol.
将实施例 2步骤 （5 ) 中的乙二胺换成己二硫醇， 可制备出化合物 E-9  Compound E-9 can be prepared by replacing ethylenediamine in step (5) of Example 2 with hexamethylenedithiol.
将实施例 2步骤 （5 ) 中的乙二胺换成己二胺， 可制备出化合物 E-10 实施例 3.含化合物的品红墨水组合物  Compound E-10 can be prepared by replacing ethylenediamine in step (5) of Example 2 with hexamethylenediamine. Example 3. Magenta ink composition containing compound
(A) 品红墨水组合物的制备  (A) Preparation of magenta ink composition
使用上述实施例所制备的化合物 E1〜E10，分别制备下表所示的组合物，经 0.45 m 膜滤器过滤， 得到本发明的水性品红墨水组合物。 另外， 添加离子交换水、 三乙醇胺 使墨水组合物的 pH值成为 8〜10、 总量达到 100重量份。 将所选染料及对照的单核染 料 Dyel、 商品染料 C.I.活性红 180水解衍生物 （简称活性红 180) 和 C.I.直接红 227 分别制作比较用的墨水组合物。 用这些墨水组合物进行喷墨打印， 并进行打印图像的 评价。  Using the compounds E1 to E10 prepared in the above examples, the compositions shown in the following Table were separately prepared and filtered through a 0.45 m membrane filter to obtain an aqueous magenta ink composition of the present invention. Further, ion-exchanged water and triethanolamine were added to adjust the pH of the ink composition to 8 to 10 and the total amount to 100 parts by weight. The selected dye and the comparative mononuclear dye Dyel, the commercial dye C.I. Reactive Red 180 hydrolyzed derivative (abbreviated as Reactive Red 180) and C.I. Direct Red 227 were respectively prepared into comparative ink compositions. These ink compositions were used for ink jet printing, and evaluation of printed images was performed.
Figure imgf000020_0001
Figure imgf000020_0001
Dye1  Dye1
组 分 含量 （重量份）  Component content (parts by weight)
本发明的双核蒽吡啶酮染料 （折 100%) 6  The binuclear pyridinone dye of the invention (100%) 6
甘油 5  Glycerin 5
尿素 5  Urea 5
2-吡咯垸酮 4  2-pyrrolidone 4
乙二醇单丁醚 2  Ethylene glycol monobutyl ether 2
异丙醇 3  Isopropanol 3
非离子表面活性剂 OP-10 0.2  Nonionic surfactant OP-10 0.2
三乙醇胺 （调节 pH) 0.2  Triethanolamine (adjusting pH) 0.2
EDTA 0.1  EDTA 0.1
杀菌剂 0.01  Fungicide 0.01
余量去离子水 补满至 100重量份 (B) 喷墨打印机： The remaining amount of deionized water is up to 100 parts by weight (B) Inkjet printer:
使用喷墨打印机 （Epson公司制造 Epson 270型打印机）， 将具有含多孔性白色无 机物的墨水受像层的高光相纸 （Epson公司制造）， 进行喷墨打印。 图像的打印样张有 密度阶段。  A high-light photographic paper (manufactured by Epson Co., Ltd.) having an ink-receiving layer containing a porous white inorganic material was subjected to inkjet printing using an ink jet printer (Epson Model 270 printer manufactured by Epson Co., Ltd.). The print sample of the image has a density stage.
(C) 打印图像的评价：  (C) Evaluation of printed images:
( 1 ) 打印图像的氙气灯耐光性试验  (1) Xenon lamp light resistance test for printed images
将经打印的佳能公司制造的光泽纸与爱普生公司制造的光泽纸的试验片， 使用氙 气灯耐候仪 Ci400(商品名称； ATLAS公司制造）， 在湿度 60%RH、 温度 24 °C的条件 下， 以 O.36W/平方公尺照度照射 50小时， 测定试验前后的色差 （ΔΕ)。 色差 （ΔΕ) 是以上述的测色***（Unterlab: GRETAG公司制造）进行测定试验前后的各 L*、 a*、 b*的值， 并由 L*、 a*、 b* 各值的试验前后的差由下述式求出：  The test piece of the glossy paper manufactured by Canon and the glossy paper made by Epson was used, and the Xenon lamp weather resistance meter Ci400 (trade name; manufactured by ATLAS) was used under the conditions of humidity 60% RH and temperature 24 °C. Irradiation was carried out for 50 hours at an illuminance of O.36 W/m 2 , and the color difference (ΔΕ) before and after the test was measured. Color difference (ΔΕ) is the value of each L*, a*, b* before and after the measurement test by the above-mentioned color measurement system (Unterlab: GRETAG), and before and after the test of each value of L*, a*, b* The difference is obtained by the following formula:
△E= ((L*的差) 2 + (a*的差) 2 + (b*的差) 2)1/2。 △E=((L* difference) 2 + (a difference of a*) 2 + (difference of b*) 2 ) 1/2 .
依照以下的基准， 以分 3个级别进行评价：  Based on the following benchmarks, it is evaluated in three levels:
ΔΕ < 10 ο  ΔΕ < 10 ο
ΔΕ < 20 Δ  ΔΕ < 20 Δ
ΔΕ > 20  ΔΕ > 20
(2) 记录图像的耐臭氧气体性试验  (2) Recording image for ozone gas resistance test
将经打印的佳能公司制造的光泽纸， 使用臭氧耐候仪 （公司制造） 在臭氧浓度 40ppm、 湿度 60%RH、 温度 24 °C的环境下放置 6小时。 与上述 （2) 相同做法所得的 试验前后的色差 （ΔΕ), 依照以下的基准分 3个级别进行评价：  The glossy paper manufactured by Canon Inc. was placed in an ozone concentration of 40 ppm, a humidity of 60% RH, and a temperature of 24 ° C for 6 hours using an ozone weather resistance meter (manufactured by the company). The color difference (ΔΕ) before and after the test obtained in the same manner as in the above (2) was evaluated in three levels according to the following criteria:
ΔΕ < 10 ο  ΔΕ < 10 ο
ΔΕ < 20 Δ  ΔΕ < 20 Δ
ΔΕ > 20  ΔΕ > 20
(3 ) 记录图像的耐湿性试验  (3) Recording image moisture resistance test
将经印刷的佳能公司制造的光泽纸与爱普生公司制造的光泽纸的试验片以恒温恒 湿器 （应用技研产业公司制造） 在 50°C、 90%RH的条件下放置 168小时， 以目视判 定试验前后的渗出性， 依以下的基准分 3个级别进行评价。  The test piece of the glossy paper manufactured by Canon and the glossy paper made by Epson was placed in a constant temperature and humidity apparatus (manufactured by Applied Technology Co., Ltd.) at 50 ° C, 90% RH for 168 hours to visually observe. The exudation property before and after the test was judged and evaluated in three levels according to the following criteria.
亳无渗出 o  亳 no oozing o
少许渗出 Δ  a little oozing Δ
渗出许多 X  Exuding many X
(D) 溶液稳定性评价： 将染料 20份、 70份与 10份乙二醇组成的***加热溶解， 冷却后， 在封闭的 50°C 恒温的条件下存贮 7天后冷却， 室温过滤， 按以下的基准分三个级别进行评价： (D) Solution stability evaluation: The system consisting of 20 parts, 70 parts and 10 parts of ethylene glycol was heated and dissolved. After cooling, it was stored under a closed 50 ° C constant temperature for 7 days, then cooled, filtered at room temperature, and divided into three levels according to the following criteria. Evaluation:
亳无沉淀 。  There is no precipitation.
少许沉淀 Δ  a little precipitation Δ
许多沉淀 X 所有结果结果示于下表:  Many precipitation X results are shown in the table below:
Figure imgf000022_0001
比较可见，本发明的双核吡啶蒽酮磺酸染料作为喷墨染料具有极为优异的稳定性、 耐光性、 耐臭氧性和耐湿性。
Figure imgf000022_0001
As can be seen, the dinuclear pyridone sulfonic acid dye of the present invention has extremely excellent stability, light resistance, ozone resistance and moisture resistance as an inkjet dye.

Claims

权 利 要 求 书 Claim
1. 一类双核蒽吡啶酮磺酸化合物或其盐， 具有通式 I的结构： A class of dinuclear pyridinone sulfonic acid compounds or salts thereof having the structure of formula I:
Figure imgf000023_0001
Figure imgf000023_0001
(I)  (I)
中：  Medium:
L是连接基团；  L is a linking group;
1^和 各自独立地选自： OH、 O(C6H5-m)(CO2H)m、 S(CH2) mSO3H、 S(CH2)mCO2H、 O(C6H5-m)(SO3H)m、 O(C10H9-m)(CO2H)m、 O(C10H9-m)(SO3H)m、 腿2、草 7)2、 SH、 SR7、 NH(C6H5-m)(CO2H)m、 NH(C6H5-m)(SO3H)m、 NH(C10H9-m)(CO2H)m、 NH(C10H9-m)(SO3H)m、 S(C6H5-m)(CO2H)m、 S(C6H5-m)(SO3H)m、 S(C10H9-m)(CO2H) S(C10H9-m)(SO3H)m ; 1^ and each independently selected from: OH, O(C 6 H 5-m )(CO 2 H) m , S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H, O(C 6 H 5-m )(SO 3 H) m , O(C 10 H 9-m )(CO 2 H) m , O(C 10 H 9-m )(SO 3 H) m , Leg 2 , Grass 7 2 , SH, SR 7 , NH(C 6 H 5-m )(CO 2 H) m , NH(C 6 H 5-m )(SO 3 H) m , NH(C 10 H 9-m )( CO 2 H) m , NH(C 10 H 9-m )(SO 3 H) m , S(C 6 H 5-m )(CO 2 H) m , S(C 6 H 5-m )(SO 3 H) m , S(C 10 H 9-m )(CO 2 H) S(C 10 H 9-m )(SO 3 H) m ;
R7是 CM垸基； R 7 is a CM group;
n是 0-2的整数；  n is an integer of 0-2;
m是 0-3的整数。  m is an integer from 0-3.
2. 权利要求 1所述的双核蒽吡啶酮磺酸化合物或其盐， 其特征在于所述的！^和 R2 各 自独立地选 自 O(C6H5-m)(CO2H)m、 S(CH2) mSO3H、 S(CH2)mCO2H 和 O(C6H5-m)(SO3H)m。 The dinuclear pyridinone sulfonic acid compound or a salt thereof according to claim 1, which is characterized in that! ^ and R 2 are each independently selected from O(C 6 H 5-m )(CO 2 H) m , S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H and O(C 6 H 5-m )(SO 3 H) m .
3.权利要求 2 所述的双核蒽吡啶酮磺酸化合物或其盐， 其特征在于所述的 L 是 -NH(CH2)pNH -、 -S(CH2)qS- 或化合物 L
Figure imgf000023_0002
The dinuclear pyridinone sulfonic acid compound or a salt thereof according to claim 2, wherein L is -NH(CH 2 ) p NH -, -S(CH 2 ) q S- or compound L
Figure imgf000023_0002
其中： p、 q是 1-18的整数。  Where: p, q are integers from 1-18.
4. 权利要求 3所述的双核蒽吡啶酮磺酸化合物或其盐，是下述化合物之一或其盐: The dinuclear pyridinone sulfonic acid compound or a salt thereof according to claim 3, which is one of the following compounds or a salt thereof:
Figure imgf000024_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000025_0002
Figure imgf000025_0003
Figure imgf000025_0001
Figure imgf000025_0002
Figure imgf000025_0003
E-8
Figure imgf000025_0004
E-8
Figure imgf000025_0004
E-9
Figure imgf000025_0005
E-9
Figure imgf000025_0005
E-10 E-10
5. 权利要求 1〜4中任一权利要求所述的双核蒽吡啶酮磺酸化合物或其盐， 其特征 在于所述的盐是相应双核蒽吡啶酮磺酸化合物的锂盐、钠盐、钾盐、铵盐或有机铵盐， 所述的有机铵盐阳离子具有通式 N+R3R4R5R6结构， 其中的 R3、 、 R5、 R6各自 独立地选自 H、 CM8垸基、 环己基、 CH2CH2OH和苄基。 The dinuclear pyridinone sulfonic acid compound or a salt thereof according to any one of claims 1 to 4, wherein the salt is a lithium salt, a sodium salt or a potassium salt of a corresponding dinuclear pyridone sulfonic acid compound. a salt, an ammonium salt or an organic ammonium salt, the organic ammonium salt cation having a structure of the formula N + R 3 R 4 R 5 R 6 wherein R 3 , R 5 , R 6 are each independently selected from H, C M8 fluorenyl, cyclohexyl, CH 2 CH 2 OH and benzyl.
6. 权利要求 5所述的双核蒽吡啶酮磺酸化合物或其盐， 其特征在于所述的盐是相 应双核蒽吡啶酮磺酸化合物的锂盐、 钠盐、 钾盐、 铵盐、 单乙醇胺盐、 二乙醇胺盐、 三乙醇胺盐、 单异丙醇胺盐、 二异丙醇胺盐或三异丙醇胺盐。 The dinuclear pyridinone sulfonic acid compound or a salt thereof according to claim 5, wherein the salt is a lithium salt, a sodium salt, a potassium salt, an ammonium salt or a monoethanolamine of the corresponding dinuclear pyridone sulfonic acid compound. Salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt or triisopropanolamine salt.
7. 权利要求 6所述的双核蒽吡啶酮磺酸化合物或其盐， 其特征在于所述的盐是相 应双核蒽吡啶酮磺酸化合物的锂盐、 钠盐或铵盐。 The dinuclear pyridinone sulfonic acid compound or a salt thereof according to claim 6, wherein the salt is a lithium salt, a sodium salt or an ammonium salt of a corresponding dinuclear pyridone sulfonic acid compound.
8. 权利要求 1所述的双核蒽吡啶酮磺酸化合物或其盐的制备方法，包括下述步骤: (i)式 III的化合物与苯甲酰乙酸酯按摩尔比 1:2〜5在有机溶剂中， 在 175〜180°C 条件下反应制备式 IV的化合物； The method for producing a dinuclear pyridinone sulfonic acid compound or a salt thereof according to claim 1, comprising the steps of: (i) a compound of the formula III and a benzoyl acetate molar ratio of 1:2 to 5; The compound of the formula IV is prepared by reacting at 175 to 180 ° C in an organic solvent;
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000026_0001
Figure imgf000026_0002
其中所述的有机溶剂是二甲苯、 二乙苯、 The organic solvent described therein is xylene, diethylbenzene,
与 DMSO按体积比 3:1组成的混合溶剂； (ii) 式 IV的化合物与发烟硫酸按摩尔比 1:50， 在 85-90 °C条件下反应 4小时制 备式 V的化合物； a mixed solvent consisting of DMSO in a volume ratio of 3:1; (ii) a compound of the formula IV is prepared by reacting a compound of the formula IV with a fuming sulfuric acid molar ratio of 1:50 at 85-90 ° C for 4 hours;
Figure imgf000027_0001
Figure imgf000027_0001
(V)  (V)
Ciii) 式 V的化合物与三聚氯氰按摩尔比 1:1在阴离子乳化剂中， 用 25 %氢氧化 钠水溶液调节 PH在 3-4， 反应 3小时得制备式 VI的化合物；  Ciii) a compound of the formula V and a cyanuric chloride molar ratio of 1:1 in an anionic emulsifier, adjusted to a pH of 3-4 with a 25 % aqueous sodium hydroxide solution, and reacted for 3 hours to prepare a compound of the formula VI;
Figure imgf000027_0002
Figure imgf000027_0002
Civ) 式 VI的化合物与 RH按摩尔比 1 :1在 25 %氢氧化钠水溶液调整 pH4-10， 于 27-30°C反应 1小时后， 继续在 40-45°C反应 1小时， 盐析得到式 VII的化合物； Civ) The compound of the formula VI is adjusted to pH 4-10 with a RH molar ratio of 1:1 in a 25% aqueous sodium hydroxide solution, and reacted at 27-30 ° C for 1 hour, and then reacted at 40-45 ° C for 1 hour, salting out. Obtaining a compound of formula VII;
Figure imgf000027_0003
Figure imgf000027_0003
其中， R 选自： OH、 O(C6H5-ra)(CO2H)m、 S(CH2) mSO3H、 S(CH2)mCO2H、 O(C6H5-m)(SO3H)m、 O(C10H9-m)(CO2H)m、 O(C10H9-m)(SO3H)m、 腿2、草 7)2、 SH、 SR7、 NH(C6H5-m)(CO2H)m、 NH(C6H5-m)(SO3H)m、 NH(C10H9-m)(CO2H)m、 NH(C10H9-m)(SO3H)m、 S(C6H5-m)(CO2H)m、 S(C6H5-m)(SO3H)m、 S(C10H9-m)(CO2H) S(C10H9-m)(SO3H)m Wherein R is selected from the group consisting of: OH, O(C 6 H 5-ra )(CO 2 H) m , S(CH 2 ) m SO 3 H, S(CH 2 ) m CO 2 H, O(C 6 H 5-m )(SO 3 H) m , O(C 10 H 9-m )(CO 2 H) m , O(C 10 H 9-m )(SO 3 H) m , leg 2 , grass 7 ) 2 , SH, SR 7 , NH(C 6 H 5-m )(CO 2 H) m , NH(C 6 H 5-m )(SO 3 H) m , NH(C 10 H 9- m )(CO 2 H) m , NH(C 10 H 9-m )(SO 3 H) m , S(C 6 H 5-m )(CO 2 H) m , S(C 6 H 5-m ) (SO 3 H) m , S(C 10 H 9-m )(CO 2 H) S(C 10 H 9-m )(SO 3 H) m
(v) 式 VII的化合物与 L按摩尔比 2:1在 25 %氢氧化钠水溶液调整 pH4-10， 在 87至 93°C反应 1小时， 后于 65±2°C下用浓盐酸调节 PH， 盐析得到式 I的化合物；  (v) The compound of the formula VII is adjusted to pH 4-10 with a molar ratio of 2:1 in a 25% aqueous sodium hydroxide solution, reacted at 87 to 93 ° C for 1 hour, and then adjusted to pH with concentrated hydrochloric acid at 65 ± 2 ° C. Salting out to give a compound of formula I;
Figure imgf000028_0001
Figure imgf000028_0001
(I)  (I)
L是 -NH(CH2)pN -、 -S(CH2)qS- 或化合物 L
Figure imgf000028_0002
L is -NH(CH 2 ) p N -, -S(CH 2 ) q S- or compound L
Figure imgf000028_0002
其中： p、 q是 1-18的整数。  Where: p, q are integers from 1-18.
9. 一种品红墨水组合物， 其特征在于： 含有权利要求 1所述的双核蒽吡啶酮磺酸 化合物或其盐。 A magenta ink composition comprising the binuclear pyridinone sulfonic acid compound according to claim 1 or a salt thereof.
10. 权利要求 9所述的品红墨水组合在喷墨打印中的应用。 10. Use of the magenta ink combination of claim 9 in ink jet printing.
PCT/CN2011/082623 2011-11-22 2011-11-22 Binuclear anthracene pyridine sulphonic acid compound or salt thereof and preparation process and use thereof WO2013075286A1 (en)

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