WO2013075287A1

WO2013075287A1 - Binuclear anthracene pyridine sulphonic acid compound containing flexible chain or salt thereof and preparation process and use thereof

Info

Publication number: WO2013075287A1
Application number: PCT/CN2011/082628
Authority: WO
Inventors: 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
Original assignee: 大连理工大学; 大连福思达专用化学有限公司
Priority date: 2011-11-22
Filing date: 2011-11-22
Publication date: 2013-05-30

Abstract

Disclosed is a binuclear anthracene pyridine sulfonic acid compound containing a flexible chain of general formula I or a salt thereof. Magenta ink compositions prepared from the compound and a salt thereof appear fresh, have a very bright tone on ink-jet recording paper, excellent water solubility, and good filterability for the membrane filter during the production of the ink composition. Furthermore, the ink composition using the compound of the present invention does not have any precipitated crystals, physical changes, or colour changes after long storage, 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

Double-core pyridinone sulfonic acid compound containing a flexible chain or salt thereof, preparation method thereof and application thereof

The present invention relates to the structure of a class of dinuclear pyridinone sulfonic acid compounds containing a flexible chain, a method of synthesizing such compounds, and a magenta ink containing such compounds 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, high-speed, and colored, and has been rapidly developed in recent years.

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 recording material, a small penetration, and excellent storage stability; in addition, the formed image must have water resistance and light resistance. , fastness to moisture resistance, etc.

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.

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.

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.

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

The prior art disclosed in CN101370882A, CN101298526A, CN101547976A, and the like.

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

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.

In order to solve the above problems, the present invention introduces a sulfonic acid group on the core of the substituted 4-aminopyridinone to increase the water solubility; on the basis of this, the two anthrapyridone sulfonic acid compound cores are linked by a group X, Increasing the molecular weight, increasing the interaction between the molecule and the coating, and improving the water resistance; the two sulfone ethyl sulfides in the dye molecule and X-forming a flexible chain, making the dye molecules less likely to aggregate and precipitate, improving ink stability The flexible group is easier to diffuse into the photographic paper coating than the rigid linking group, improving water resistance and weather resistance.

In order to solve the above problems, the present invention first provides a class of a dinuclear pyridinone sulfonic acid compound or a salt thereof having a flexible chain having the structure of the formula I:

in:

X is a linking group;

n is an integer of 0-2.

The above-mentioned flexible chain-containing dinuclear pyridone sulfonic acid compound of the present invention or a salt thereof, wherein the linking group X is preferably a fluorenyl group or a sulfonic acid group-substituted phenyl group. More preferably ((:!^^ or ?^disulfonic acid group -1,4 phenyl group; wherein 111 is an integer of 2 to 6).

Most preferably, the flexible chain-containing dinuclear pyridone sulfonic acid compound of the present invention or a salt thereof is selected from the following compounds Object (M1-

M5

M6

The flexible chain-containing dinuclear pyridone sulfonic acid compound or a salt thereof according to the present invention, wherein the salt is a lithium salt, a sodium salt, a potassium salt or an ammonium salt of a dinuclear pyridinium sulfonic acid compound containing a flexible chain. a salt or an organic ammonium salt 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, d _-18 alkyl, ring Hexyl, CH ₂ CH ₂ OH and benzyl.

Preferably, 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 monoisopropanolamine salt, a diisopropanolamine salt or the corresponding compound. Triisopropanolamine salt.

Most preferably, the salt is a lithium salt, a sodium salt or an ammonium salt of a corresponding dinuclear pyridone sulfonic acid compound containing a flexible chain.

Another object of the present invention is to provide a process for producing the above-mentioned flexible chain-containing dinuclear pyridone sulfonate compound or a salt thereof of the present invention, comprising the steps of:

(i) A compound of the formula II or formula II' is reacted with HS-X-SH at 55 to 60 ° C and a pH of 8 to 9 for 4 hours to prepare a compound of the formula III:

II I

Wherein X is a linking group;

(ii) a compound of the formula III is prepared by reacting a compound of the formula III with a benzoyl acetate molar ratio of 1:4 to 10 in an organic solvent at 135 to 140 ° C;

IV

The organic solvent is xylene, diethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, DMF or a mixed solvent of the above solvent and DMSO in a volume ratio of 3:1;

(iii) A compound of the formula IV is prepared by sulfonating a compound of the formula IV with 5 to 20% of fuming sulfuric acid at 70 to 75 ° C for 5 hours.

A further object of the present invention is to provide a magenta ink composition comprising the above-described flexible chain-containing 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 containing a flexible chain in the magenta ink composition is from 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 invention introduces an electron-absorbable water-soluble group sulfonic acid group on the anthracene ring of the dinuclear pyridone, which can not only reduce the electron cloud density of the molecule, improve the resistance to photooxidation and ozone oxidation, but also improve the solubility of the dye. To enhance the stability of the dye in the ink; on the basis of this, the two fluorenone sulfonate sulfonic acid compound cores are linked by a group X to increase the molecular weight, increase the interaction between the molecules and the coating, and improve the water resistance. The two sulfone ethyl sulfides in the dye molecule and X form a flexible chain, making the dye molecules less likely to aggregate and precipitate, improving ink stability; the flexible group is easier to coat the paper than the rigid linking group Internal diffusion, improve water resistance and weather resistance; The blue dye derivative of the existing commercial bromine is used as a basic raw material for synthesis, and the synthesis is convenient and the cost is low.

The magenta ink composition prepared by the compound of the formula (I) of the present invention and a salt thereof exhibits vividness and extremely high color tone on an ink jet recording paper, and is excellent in water solubility, and is in the process of producing an ink composition. Among them, the filterability to the filter is good. Further, the ink composition of the present invention using the compound does not precipitate crystals, physical changes, color changes, etc. after storage for a long period of time, and has 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, even if it is printed on the surface of the inkjet paper (film) such as photo quality, coated with inorganic particles. When the material is obtained, the fastness to light resistance, ozone resistance, moisture resistance, and the like is good, and the long-term storage of the image is stable. detailed description

this invention

In the formula I, X is a C?o fluorenyl group or a sulfonic acid group substituted phenyl group.

Preferably ((:!^^ or 2,5-disulfonic acid group -1,4 phenyl; m is an integer of 2-6;

Most preferred is (CH ₂ ) 4 or (CH ₂ ) ₆ .

n is an integer of 0-2.

As used herein, "mercapto" refers to a straight or branched fluorenyl group.

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; on the basis of this, the two anthrapyridone sulfonic acid compound cores are linked by a group X, Increasing the molecular weight, increasing the interaction between the molecule and the coating, and improving the water resistance; the two sulfone ethyl sulfides in the dye molecule and X-forming a flexible chain, making the dye molecules less likely to aggregate and precipitate, improving ink stability The flexible group is easier to diffuse into the photographic paper coating than the rigid linking group, improving water resistance and weather resistance.

The compound of formula I is in practical use, usually in the form of a cationic salt, which is a lithium, sodium, potassium, ammonium or organic ammonium salt of the corresponding compound, said organic ammonium salt having a pass A structure of the formula N ⁺ R ₃ R4R ₅ R ₆ wherein R ₃ , R ₄ , R ₅ , R ₆ are each independently selected from the group consisting of 11, C _1-18 fluorenyl, cyclohexyl, CH ₂ CH ₂ OH, and benzyl.

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 monoisopropanolamine salt, a diisopropyl ester of the corresponding compound. Alcoholamine salt or triisopropanolamine salt. Among them, a lithium salt, a sodium salt or an ammonium salt is most preferred.

The method for preparing a flexible chain-containing dinuclear pyridinone sulfonic acid compound of the formula I, using a mononuclear compound II or hydrazine as a basic raw material, reacts with HS-X-SH under alkaline conditions to form a general compound in an aqueous solution. III, which is then cyclized in an organic solvent to form a compound of the formula IV, IV and sulfonated with fuming sulfuric acid to give the compound of the formula I. The salt is then converted to form a salt.

In the ring-forming reaction of formula III, the reaction of the compound (formula III) with benzoyl acetate forms compound IV The reaction conditions are as follows: 1 compound III and benzoyl acetate (such as methyl ester, ethyl ester, propyl ester, isopropyl ester) according to a molar ratio of 1: 4-10 in an organic solvent, at 135 to 140 ° C conditions The next reaction.

The molar ratio of the compound III to the benzoyl acetate is preferably 1:6.

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. 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, oxalic acid Lithium, 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, preferably 1: 0.5 to 6.

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.

After completion of the reaction, the mixture was cooled to precipitate an intermediate (Formula IV). 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.

The sulfonation 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 liquid chromatography or thin layer chromatography. After completion of the reaction, the sulfonated product was poured into ice water with stirring, and stirred for 0.1 to 1 hour. Then, ammonium chloride or sodium chloride is added for multiple salting out, cooled, and filtered to obtain a compound of the formula I.

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.

In a preferred embodiment of the magenta ink composition of the present invention, the mass percentage of inorganic impurities is not More than 1% of the total mass of the non-solvent component, the dye may be desalted using 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. In the composition, the content of the dinuclear pyridone compound containing a flexible chain is generally 0.1 to 20% in the ink composition, 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.; ₄ ,N-N An amide of a carboxylic acid such as methylformamide or N,N-dimethylacetamide; a lactam such as 2-pyrrolidone or N-methyl-2-pyrrolidone; 1,3-dimethylmorpholine- a cyclic nitrogen-containing solvent such as 2-ketone or 1,3-dimethylhexahydropyrimidin-2-one; a ketone or a ketone such as acetone, methyl ethyl ketone or 2-methyl-2-hydroxypentan-4-one Alcohol; a 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; CM mercapto ether of polyhydric alcohol such as diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; γ-butyrolactone or dimethyl sulfoxide . 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.

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. .

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 sodium benzoate and the like. The pH adjuster is not affected by the adverse effects of the conditioned ink, and any substance can be used as long as the pH 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.

Examples of the chelating agent 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, ε-caprolactam, diethyl carbonate and the like.

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.

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.

In the above production method, the order of dissolution of each component is not particularly limited. The dye can be dissolved in water beforehand Or the aqueous solvent may be dissolved by adding an ink preparation agent, or an aqueous solvent or an ink preparation agent may be added after the dye is dissolved in water to dissolve it. It can also be different from this order. Further, an aqueous composition 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 micrometer to 0.1 micrometer, preferably from 0.8 micrometer to 0.2 micrometer.

The water-soluble ink composition of the water-soluble flexible chain-containing 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 has excellent resistance to water, sunlight, ozone and friction, 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. 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.

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.

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.

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 the respective ink cartridges and are respectively mounted on The inkjet printer is used at a predetermined position. 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.

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 are provided to enable those of ordinary skill in the art to understand the invention. Example 1. Preparation of Compound Ml

(1) 125.2 parts of commercial dye (11-1) is added to 500 parts of water and stirred to dissolve, then 13.5 parts of 1,6-hexanedithiol, ie HS(CH ₂ ) ₆ SH, is added, and the temperature is gradually increased to 55-60 °. C, 20% aqueous sodium hydroxide solution was continuously added dropwise at the time of temperature rise, and pH 6-7 was maintained until the pH was constant at pH 9, at which time the dye was precipitated, filtered, and dried to obtain 110 parts of the derivative M1-B. Maximum absorption in water 603nm, mass spectrum m/z (-): 558.0 ([M-2H] ² 72]), 1117.1 ([MH]" ¹ ), 1139.1 ([M-2H+Na]" ¹ ), intermediate dye The product (calculated as M = H free sulfonic acid SO ₃ H) The most accurate molecular mass number M was 1118.1.

(2) In 300 parts of xylene, 100 parts of dimethyl sulfoxide was added, and 128 parts of blue dye Ml-B, 7.5 parts of sodium carbonate, and 180 parts of ethyl benzoylacetate were sequentially placed while stirring. Warm up. The reaction was carried out at 135 to 140 ° C for 10 hours, during which the ethanol and water formed in the reaction were azeotropically distilled out of the reaction system, and the color gradually changed from blue to purple, and the liquid chromatograph detected the completion of the reaction (about required) 10 hours). After cooling, 400 parts of isopropanol was added at 30 ° C and stirred for 30 minutes, and the precipitate was separated by filtration, and the resulting precipitate was washed with 500 parts of isopropyl alcohol and dried. 152 parts of pale red-purple crystals were obtained. The sodium salt of the formula (M1-R) is represented by a free sulfonic acid group. The maximum absorption in water is 548 nm, mass spectrum m/z (-): 686.0 ([M-2H] ² 72]), 1373.2 ([MH] ^_1 ). The intermediate dye product (calculated as free sulfonic acid SO ₃ H) has the most accurate molecular mass number M of 1374.2.

M1 -R M = Na

(3) In 450 parts of 95.0% sulfuric acid, 380.0 parts of 50% fuming sulfuric acid was added under cooling and stirring to prepare 830 parts of 10% fuming sulfuric acid. After cooling, 152 parts of the compound represented by the above formula (M1-R) was added at a temperature not higher than 20 ° C and the temperature was raised. The sulfonation reaction was carried out at 70 to 75 ° C for 5 hours. After cooling, the reaction solution was slowly poured into 1400 parts of ice water under stirring, and the temperature was controlled below 40 °C. After adding water to 2500 parts of filtration to remove insolubles, water was added to make the total amount of the solution 3000 parts. 300 parts of sodium chloride was added at 40 to 45 ° C, and then salted out for 1 hour, filtered to obtain a solid of a purple dye, and dried to obtain 135 parts of a M1 dye (sodium salt, M1 is represented by a free sulfonic acid). The filtrate was adjusted to a pH of 9-10 with 30% sodium hydroxide in an ice water bath, and about 2600 parts of a solution containing 125 parts of dye (Ml) was obtained after salt removal. The maximum absorption wavelength of the dye M1 in water is 525 nm. Mass Spectrometry (EI-MS) m/z (-): 422.5 ([M-4H] ⁴ 74), 563.7 ([M-3H] ³ 73, 846.0 ([M-2H] ² 72. Dye Ml (with free sulphur) Acid SO ₃ H meter) The most accurate molecular mass number M is 16

Example 2. Preparation of Compounds M3, M4, M5, M6

In the same manner as in Example 1, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,4-benzenedithiol, respectively, using different bases. The magenta dyes M3, M4, M5, and M6 having the structural formula (1-1) were prepared by salting out MOH and MC1. The linker X and the sulfonic acid counter ion are shown in Table 1.

Table 1

Example 3. Preparation of Compound M2

(1) CI Reactive Blue 19 Commercial Dyes (Structure II-2) 125.2 parts are added to 500 parts of water and stirred to dissolve, and then 13.5 parts are added to the 1,6-hexanedithiol, and the temperature is gradually raised to 55-60 ° C. A 20% aqueous solution of lithium hydroxide was continuously added dropwise, maintaining pH 6-7 until the pH was constant at pH 9, filtered, and the filter cake was washed with a 10% aqueous lithium chloride solution and dried to give 112 parts of the derivative M2-B. Maximum absorption in water 603nm, mass spectrum m/z(-): 558.0 ([M-2H] ² 72]), 1117.1 ([MH] ^-1 ), 1139.1 ([M^H+Na]" ¹ )^ intermediate dye The product M2-B (calculated as free sulfonic acid SO ₃ H) is the most accurate

M2-B M = Li (2) In 300 parts of xylene, 100 parts of dimethyl sulfoxide was added, and 128 parts of the compound of the formula M2-B, 7.5 parts of sodium carbonate, and 180 parts of ethyl benzoylacetate were sequentially placed while stirring. Warm up. The reaction was carried out at 135 to 140 ° C for 10 hours, during which the ethanol and water formed in the reaction were azeotropically distilled out of the reaction system, and the color gradually changed from blue to purple, and the liquid chromatograph detected the completion of the reaction (about required) 10 hours). After cooling, 400 parts of isopropyl alcohol was added at 30 ° C and stirred for 30 minutes, and the precipitate was separated by filtration, and the obtained precipitate was washed with 500 parts of isopropyl alcohol and dried to obtain 155 parts of pale red-purple crystal. It is represented by a lithium salt as the formula M2-R. Maximum absorption in water 552nm, mass spectrum m/z (-): 686.0 ([M-2H] ² 72]), 1373.2 ([Μ-ΗΓ^ intermediate dye product M2-R (as free sulfonic acid SO ₃ H) The accurate molecular mass number M is 1374.2.

M2-R M = Li

(3) In 450 parts of 95.0% sulfuric acid, 380.0 parts of 50% fuming sulfuric acid was added under cooling and stirring to prepare 830 parts of 10% fuming sulfuric acid. After cooling, 155 parts of the compound represented by the above formula (M2-R) was added at a temperature not higher than 20 ° C and the temperature was raised. The sulfonation reaction was carried out at 70 to 75 ° C for 5 hours. After cooling, the reaction solution was slowly poured into 1400 parts of ice water under stirring, the temperature was controlled below 40 ° C, 660 parts of calcium hydroxide was slowly added, stirred for 1 hour, filtered, and the filter cake was washed with 600 ml of water, and the filtrate was placed in an ice water bath. The pH was adjusted to 9-10 with 30% sodium hydroxide, and about 2600 parts of the dye containing 130 parts (M2) were obtained after desalting. The maximum absorption wavelength of dye M2 in water is 528 nm. Mass Spectrometry (EI-MS) m/z (-): 422.5 ([Μ-4Η] ⁴ 74), 563·7 ([Μ-3Η] ³ 73, 846·0 ([Μ-2Η] ² 72. Dye Ml (Based on free sulfonate SO ₃ H) The most accurate molecular mass number M is 1694.0.

M2 M = Li Example 4. Preparation of Compounds M7, M8, M9, M10 In the same manner as in Example 3, respectively, using 1,2-ethanedithiol, 1,3-propanedithiol, and 1,4-butyl Dithiol, 1,4- The benzenedithiol was subjected to salting out with different base MOH and MCI to obtain M7, M8, M9, M10 having the structural formula (1-2). The linker X and the sulfonic acid counter ion are shown in Table 2.

Example 5. Compound-containing magenta ink composition

(A) Preparation of magenta ink composition

Using the compounds M1 to M10 prepared in the above Examples, the compositions shown in Table 3 below were separately prepared and filtered through a 0.45 μm membrane filter to obtain an aqueous magenta ink composition of the present invention. Further, ion-exchanged water or triethanolamine was added so that the ink composition had a pH of 8 to 10 and a total amount of 100 parts by weight. The selected dye and the control mononuclear dye Dyel, the commercial dye CI. 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 inkjet printing, and evaluation of printed images was performed.

Dye1 table 3

(B) Inkjet printer:

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) Evaluation of printed images:

(1) Xenon lamp light resistance test for printed images

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* difference) ² + (a difference of a*) ² + (difference of b*) ² ) ^1/2 .

Based on the following benchmarks, it is evaluated in three levels:

ΔΕ < 10 ο

ΔΕ < 20 Δ

ΔΕ > 20

(2) Recording image for ozone gas resistance test

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). Obtained from the same practice as (2) above The color difference (ΔΕ) before and after the test was evaluated in three levels according to the following criteria:

ΔΕ < 10 ο

ΔΕ < 20 Δ

ΔΕ > 20

(3) Recording image moisture resistance test

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 no oozing o

a little oozing Δ

Exuding many X

(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: No precipitation.

a little precipitation Δ

Many precipitates X

The results of all results are shown in the table below:

As can be seen, the flexible chain-containing dinuclear pyridone sulfonic acid dye of the present invention has extremely excellent stability, light resistance, ozone resistance and moisture resistance as an ink jet dye.

Claims

Soft

in:

X is a linking group;

n is an integer of 0-2.

The soft chain-containing dinuclear pyridone sulfonic acid compound or a salt thereof according to claim 1, wherein the X is a mercapto group or a sulfonic acid group-substituted phenyl group.

The flexible chain-containing dinuclear pyridinone sulfonic acid compound or a salt thereof according to claim 2, wherein the X is ((:!!^ or 2,5-disulfonic acid-1,4) Phenyl group;

Wherein 111 is an integer of 2 to 6.

The flexible chain-containing dinuclear pyridone sulfonic acid compound or a salt thereof according to claim 3, which is one of the following compounds or

M2

The flexible chain-containing dinuclear pyridinone sulfonic acid compound or a salt thereof according to any one of claims 1 to 4, wherein the salt is a dinuclear pyridinone sulfonic acid compound containing a flexible chain. Lithium salt, sodium salt, potassium salt, ammonium salt or organic ammonium salt,

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 H, C _M8 fluorenyl, cyclohexyl, CH ₂ CH ₂ OH and benzyl.

The flexible chain-containing dinuclear pyridone 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 salt of the corresponding compound. Diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt or triisopropanolamine salt.

The flexible chain-containing dinuclear pyridone 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 the corresponding compound.

The method for producing a flexible chain-containing dinuclear pyridinone sulfonic acid compound or a salt thereof according to claim 1, comprising the steps of:

II I

Wherein X is a linking group;

(ii) a compound of the formula III is prepared by reacting a compound of the formula III with a benzoyl acetate molar ratio of 1:4 to 10 in an organic solvent at a temperature of 135 to 140 'C;

IV

A magenta ink composition comprising the flexible chain-containing dinuclear pyridinone sulfonic acid compound according to claim 1 or a salt thereof.

10. Use of the magenta ink combination of claim 9 in ink jet printing.