JP2006328093A - Compound, manufacturing method, ink and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye (compound) having high fluorescence intensity which has good water solubility in water, very superior water resistance against paper (especially ordinary paper) and can cope with from printing to be visually recognizable by adjusting the dye concentration to printing to be readable with fluorescence emission by irradiation with certain specified ultraviolet rays, and an ink containing the same. <P>SOLUTION: The compound in the form of a free-acid is represented by formula (1) (wherein m and n are each independently 1 or 2). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a compound, an ink using the compound, an ink jet recording method using the ink, a colored body, and a manufacturing method.

Fluorescent dyes are used not only for cloth and paper dyeing, but also recently for special inks for distinguishing between genuine and counterfeit products. In fact, by using a fluorescent color material for the ink, it is possible to emit fluorescent light and give information other than visible information by irradiating with appropriate ultraviolet light. As a result, the fluorescent ink can impart two types of information transmission (visible light and fluorescence).

In particular, among inks having fluorescence, an ink containing water has great advantages in terms of ease of handling and manufacturing.

Examples of water-soluble dyes that exhibit fluorescence used in fluorescent ink include Basic Red 1, Basic Red 2, Basic Red 9, Basic Red 12, Basic Red 13, Basic Red 14, Basic Red 17, Basic Violet 1, and Basic Violet 3 Basic Violet 7, Basic Violet 10, Basic Violet 11: 1, Basic Violet 14, Acid Red 51, Acid Red 52, Acid Red 92, Acid Red 94, Direct Yellow 11, Direct Yellow 24, Direct Yellow 26, Direct Yellow 87 , Direct Yellow 100, Direct Yellow 132, Direct Yellow 147, Direct Orange 26, Direct Orange 2 , Direct Orange 29: 1, Direct Orange 46, Direct Red 1, Direct Red 17, Direct Red 239, Direct Red 240, Direct Red 242, Direct Red 254, and the like.

Examples of fluorescent ink coating and printing methods include ordinary bar coater coating, air knife coating, gravure coating, offset printing, flexographic printing, screen printing, and ink jet printing. Because of its low cost, high-speed recording capability, low noise during recording, and easy color recording, it is rapidly spreading and further developing. Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method for discharging bubbles, a method for generating bubbles in ink by discharging heat, a method for discharging droplets, a method using ultrasonic waves, a method for sucking and discharging droplets by electrostatic force, and the like. In fact, water-soluble ink is a representative example of ink that is very suitable for ink jet recording.

For dyes used in such water-soluble fluorescent inks suitable for ink jet recording, they have excellent durability against water and chemicals, have good fixability to recording materials and are difficult to bleed, It is required to have excellent storage stability, non-toxicity, excellent water resistance and friction resistance, high fluorescence intensity, and availability at low cost. In particular, since water-soluble coloring materials are used, water resistance with an inexpensive medium such as plain paper is regarded as most important as durability.

Japanese Patent Laid-Open No. 9-302293 Japanese Patent No. 2737833 JP 11-152436 A JP 2003-192962 A JP 2003-285432 A Japanese Patent Publication No. 37-12826

The purpose of the present invention is that it has good solubility in water, water resistance to paper (especially plain paper) is extremely excellent, and irradiates a specific ultraviolet light from a print that can be visually recognized by adjusting the dye concentration. Accordingly, it is an object of the present invention to provide a dye (compound) having high fluorescence intensity that can cope with printing that can be read by fluorescence emission, and an ink containing the same.

As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.
That is, the present invention is (1) a compound represented by the following formula (1) in the form of a free acid.

(In formula (1), m and n each independently represent 1 or 2.)

(2) The compound represented by the formula (1) according to (1), wherein the content of anions of Cl ^- and SO ₄ ^2- is 1% by mass or less.

(3) Ink containing the compound of (1) or (2) (4) Ink according to (3) containing water and a water-soluble organic solvent (5) For inkjet recording (3) or (4) Ink described in

(6) In an ink jet recording method in which ink droplets are ejected in accordance with a recording signal to perform recording on a recording material, the ink according to any one of (3) to (5) is used. Inkjet recording method (7) The inkjet recording method according to (6), wherein the recording material is an information transmission sheet (8) A sheet on which the information transmission sheet is surface-treated, and white inorganic pigment particles on the support The ink jet recording method according to (7), which is a sheet having an ink image-receiving layer containing

(9) A container (10) containing the ink according to any one of (3) to (5) (10) Any one of the inkjet printers (11), (3) to (5) having the container according to (9) Colored body colored with the ink according to one item

(12) A process for producing the compound according to (1)

The compound of the present invention is extremely excellent in water solubility, has the characteristics of good filterability with respect to a membrane filter during the ink production process, and has high fluorescence intensity. In addition, the ink using the compound of the present invention is free from crystal precipitation, physical property change, color change and the like after long-term storage, and has good storage stability. Further, a printed matter using the ink of the present invention for inkjet recording is excellent in water resistance and moisture resistance, and particularly excellent in water resistance on plain paper. Therefore, the ink of the present invention is extremely useful as a fluorescent ink for ink jet recording.

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

(In formula (1), m and n each independently represent 1 or 2.)

The salt of the compound represented by the formula (1) is an inorganic or organic cation salt. Examples of the salt include alkali metal salts such as lithium salt, sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, or ammonium salt represented by the following formula (2).

(In formula (2), X _{1 to} X ₄ each independently represents a hydrogen atom, an alkyl group, a hydroxyalkyl group or a hydroxyalkoxyalkyl group.)

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

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

The salt can be obtained, for example, as a wet cake by adding salt to a reaction solution or a cake containing a target product or a dried product dissolved in water, salting out and filtering. If the wet cake is dissolved again in water and then the crystals obtained by adding hydrochloric acid to adjust the pH to 1 to 2 are filtered, the crystals can be obtained in the form of the free acid (or partly as a sodium salt). Can do. Further, while the wet cake of the free acid is stirred with water, for example, potassium hydroxide, lithium hydroxide, aqueous ammonia, organic amine or the like is added to make it alkaline, each is represented by the corresponding formula (1). The potassium salt, lithium salt, ammonium salt and organic amine salt of the compound are obtained. Among these salts, lithium, potassium, ammonium and sodium salts are particularly preferable as described above.

Although it does not specifically limit as a suitable example of the compound shown to Formula (1), Specifically, a structure like the following Table 1 is mentioned. For convenience, in Table 1, the position of the sulfonic acid is shown as A ring and B ring as in the following formula (3). m and n each independently represent 1 or 2. The substitution position of sulfonic acid is also as defined by the following formula (3).

Table 1 Compound examples
No Position of sulfonic acid group on A ring Position of sulfonic acid group on B ring
1 2 4
2 4 4
3 2 4,6
4 4,6 4

The compound represented by Formula (1) of this invention is manufactured by the following method, for example.
That is, the following formula (4)

Diazotization is carried out by adding sodium nitrite to the compound represented by Then, the compound represented by following formula (6) is obtained by adding aminonaphthalene shown by following formula (5), and adding sodium carbonate.
The compound of the above formula (4) is obtained by coupling diazotized 4-nitro-4′-aminostilbene-2,2-disulfonic acid and aminonaphthalenesulfonic acid, oxidizing this, triazolizing it, Obtained by known methods of reduction. As aminonaphthalenesulfonic acid, 3-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid and the like can be used as appropriate.

Subsequently, the compound of formula (1) triazotized by reacting the azo compound of formula (6) and sodium hypochlorite in water usually at pH 8-13, usually 30 ° C-100 ° C, 0.1-12 hours. Is obtained.

The compounds of the present invention are suitable for dyeing natural and synthetic fiber materials or blends, and these compounds are also suitable for the production of writing inks and ink jet recording inks.

A compound having a small content of anions such as Cl ^- and SO ₄ ^2- contained in the compound represented by the above formula (1) is preferable, and the standard of the content is Cl ^- and SO ₄ ^{2- in the} compound. The total content is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and 1% by mass or less in the ink. Cl ^- and preparing the compounds of SO ₄ ^2-less invention, a dried product or a wet cake of a compound of the conventional method or the present invention using a reverse osmosis membrane for example stirred in a mixed solvent of alcohol and water, What is necessary is just to desalinate by methods, such as filtration and drying. The alcohol used is a lower alcohol having 1 to 4 carbon atoms, preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol, ethanol or 2-propanol. Further, in the desalting treatment with alcohol, a method of heating to near the boiling point of the alcohol used and then cooling to desalinate can be employed. The content of Cl ^- and SO ₄ ^2- is measured, for example, by ion chromatography.

When the ink of the present invention is used as an ink for ink jet recording, an ink containing a low content of heavy metals (ions) such as copper, zinc and iron, metals such as calcium and silica (cations), etc. contained in the compound is used. Is preferred. The standard of the content is, for example, about 500 ppm or less for each of heavy metals (ions) such as copper, zinc and iron, and metals (cations) such as calcium and silica in the purified and dried product of the compound. Particularly for copper, it is preferably 100 ppm or less. The contents of heavy metals (ions) and metals (cations) are measured by ion chromatography, atomic absorption, or ICP (Inductively Coupled Plasma) emission analysis.

The ink of the present invention is prepared using water as a medium. The ink of the present invention contains 0.0001 to 10% by mass of the compound of the formula (1) having the above-described conditions obtained as described above. The ink of the present invention further contains a water-soluble organic solvent as necessary within a range that does not impair the effects of the present invention. Water-soluble organic solvents are used as dye solubilizers, drying inhibitors (wetting agents), viscosity modifiers, penetration enhancers, surface tension modifiers, antifoaming agents, and the like. Other ink preparation agents include, for example, antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventive agents, UV absorbers, viscosity adjusters, dye solubilizers, antifading agents, emulsion stabilizers, surface tension adjusters, Well-known additives, such as an antifoamer, a dispersing agent, a dispersion stabilizer, are mentioned. The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass, preferably 0 to 15% by mass.

Examples of water-soluble organic solvents that can be used in the present invention include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol, N, N-dimethyl. Carboxamide such as formamide or N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2- Heterocyclic ketones such as ON, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or cyclic ethers such as ketoalcohol, tetrahydrofuran, dioxane, ethylene glycol, 1,2- or 1,3 -Propylene glycol, 1,2-ma Has (C2-C6) alkylene units such as 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. Monomers, oligomers or polyalkylene glycols or thioglycols, polyols (triols) such as glycerin, hexane-1,2,6-triol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether or triol Multivalent such as ethylene glycol monomethyl ether or triethylene glycol monoethyl ether (C1 -C4) alkyl ethers of alcohol, gamma-butyrolactone or dimethyl sulfoxide and the like.

Of these, preferred are isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone and N-methyl-2-pyrrolidone, and more preferred are isopropanol, glycerin, diethylene glycol and 2-pyrrolidone. is there. These water-soluble organic solvents are used alone or in combination.

Examples of the antiseptic / antifungal agent include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzthiazole, nitrityl, pyridine, 8- Oxyquinoline, benzothiazole, isothiazoline, dithiol, pyridine oxydide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, Examples thereof include brominated indanone compounds, benzyl bromoacetate compounds, and inorganic salt compounds. An example of the organic halogen compound is sodium pentachlorophenol, an example of the pyridine oxido compound is sodium 2-pyridinethiol-1-oxide, and an example of the inorganic salt compound is anhydrous sodium acetate. Examples of the isothiazoline-based compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Can be mentioned. Other antiseptic / antifungal agents include sodium sorbate, sodium benzoate, and the like (for example, Proxel GXL (S), Proxel XL-2 (S), etc. manufactured by Avecia).

As the pH adjuster, any substance can be used as long as it can control the pH of the ink within the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. For example, alkanolamines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. And carbonates.

Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate and the like. Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

Examples of the ultraviolet absorber include a compound that emits fluorescence by absorbing ultraviolet rays typified by benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, or benzoxazole compounds, so-called fluorescence. Brighteners can also be used.
Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like.

The anti-fading agent is used for the purpose of improving image storage stability. As the antifading agent, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like.

Examples of the surface tension adjusting agent include a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant. Examples of anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxyalkyl ethers Sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkyl allyl sulfone hydrochloride, diethyl sulfosuccinate And dioctyl sulfosuccinate of diethylhexylsilsulfosuccinate. Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives. Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ethers such as alkyl ethers, polyoxyallylalkyl alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquis Esters such as oleate, polyoxyethylene monooleate, polyoxyethylene stearate, 2, 4, 7, -Acetylene glycol systems such as tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol (for example, Surfinol (registered trademark) 104E, 104PG50, 82, 465, Orphine STG, etc., manufactured by Nissin Chemical Co., Ltd.). These ink preparation agents are used alone or in combination. The surface tension of the ink of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m. The viscosity of the ink of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less.

As the antifoaming agent, a fluorine-based or silicone-based compound is used as necessary.

In the production method of the ink of the present invention, there is no particular limitation on the order in which the respective drugs are dissolved. In preparing the ink, the water to be used is preferably one having few impurities such as ion exchange water or distilled water. Furthermore, the obtained ink may be subjected to microfiltration using a membrane filter or the like, if necessary, to remove impurities. It is particularly preferable to perform microfiltration when used as an ink for an ink jet printer. The pore diameter of the filter for performing microfiltration is usually 1 to 0.1 microns, preferably 0.8 to 0.2 microns.

The inks of the present invention are suitable for use in printing, copying, marking, writing, drafting, stamping, or recording methods, particularly ink jet printing methods.

In the ink jet recording method of the present invention, energy is supplied to the ink produced by the above method, and a known image receiving material, that is, plain paper, resin-coated paper, ink jet exclusive paper, glossy paper, glossy film, and electrophotographic co-paper. Images are formed on fibers, fabrics (cellulose, nylon, wool, etc.), glass, metal, ceramics, leather, etc.

When forming an image, a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing for applying the polymer latex to the recording material may be before, after, or simultaneously with the application of the colorant. Alternatively, it may be in an ink or may be used as a liquid material of a polymer latex alone.

The recording material (medium: particularly recording paper and recording film) used for ink jet printing using the ink of the present invention will be described below. Examples of the non-recording material include information transmission sheets such as paper and film, fibers, cloth, leather, and the like. The support in paper and film usually consists of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, and CGP, and waste paper pulp such as DIP. If necessary, pigment In addition, additives such as a binder, a sizing agent, a fixing agent, a cation agent, and a paper strength enhancer mixed with each other and produced by various apparatuses such as a long net paper machine and a circular net paper machine can be used. In addition to these supports, synthetic paper and plastic film sheets may be used. The thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² . The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used as the support. It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support may contain a pigment or an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, and the like. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer. The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

As the mordant added to the ink receiving layer, for example, a polymer mordant is used.

The water-proofing agent is effective for making the image water-resistant. As these water-proofing agents, cationic resins are particularly preferable. Examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine-based antioxidants, benzophenone-based and benzotriazole-based ultraviolet absorbers, and the like. Of these, zinc sulfate is preferred.

The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin). Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. Polymer latex is used for the purpose of improving film properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

These recording papers and recording films are generally called plain paper, high-quality paper, coated paper, processed paper, exclusive inkjet paper, glossy paper or glossy film. For example, Pictrico (manufactured by Asahi Glass Co., Ltd.), Color BJ Paper, high-grade exclusive paper, color BJ photo film sheet, super photo paper, professional photo paper (all manufactured by Canon Inc.), color image jet paper (manufactured by Sharp Corporation), PM photo paper, gloss for exclusive use of Super Fine It is commercially available as a film (all manufactured by Epson Corporation), Picta Fine (manufactured by Hitachi Maxell Corporation), and the like.

The colored body using the ink of the present invention represents a color obtained by printing the ink prepared by the above method with an ink jet printer.

In order to record on the recording material by the ink jet recording method of the present invention, for example, a container containing the above-mentioned ink may be set at a predetermined position of the ink jet printer and recorded on the recording material by an ordinary method. Examples of the ink jet printer include a piezo printer using mechanical vibration and a bubble jet (registered trademark) printer using bubbles generated by heating.

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

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by the following examples. Here, the structural formula of the compound in each step is expressed in the form of a free acid. In the text, “parts” and “%” are based on mass unless otherwise specified.

Example 1 (synthesis)
200 parts of the compound of (7) is heated and dissolved at 1800 parts of water at 60 to 70 ° C., 51 parts of 40% aqueous sodium nitrite solution is added, and this solution is diluted with 500 parts of water to a solution of 80 parts of 35% hydrochloric acid. The solution was added dropwise at room temperature to diazotize.

After adding 59 parts of 2-naphthylamine-6-sulfonic acid to the diazo suspension obtained by the above reaction at room temperature, the pH value is maintained at 6.0 to 6.5 by adding sodium carbonate for 1 hour. Stirring gave 205 parts of compound (8).

The compound of the formula (8) obtained above was heated to 60 ° C., and the pH value was adjusted to 11.5 by adding sodium hydroxide. 240 parts of 12% sodium hypochlorite aqueous solution was added here, and it heated up at 70 degreeC. After stirring at 70 ° C. for 1 hour, the pH value was adjusted to 8.0 by addition of 35% hydrochloric acid, salting out with sodium chloride, filtration and drying to obtain 165 parts of the compound of the formula (9) of the present invention.
The resulting compound was desalted using a reverse osmosis membrane to reduce the inorganic content. It was the maximum absorption wavelength (λmax: 380.5 nm) of this compound in water.
Metal (ion) content; ICP emission analysis data: copper 10 ppm or less, calcium 10 ppm or less, magnesium 10 ppm or less, aluminum 10 ppm or less, iron 10 ppm or less, silica 10 ppm or less. Anion; ion chromatography: chloro ion 100 ppm, sulfate ion 100 ppm or less.

Example 2 (Preparation of ink composition and test example)
(A) Preparation of ink-1
A liquid having the following composition was prepared, and each ink-jet aqueous ink composition was obtained by filtering through a 0.45 μm membrane filter. Moreover, ion-exchange water was used for water. Water and caustic soda were added so that the ink composition had a pH of 8 to 10 and a total amount of 100 parts.

Table 2
1) Ink 2) Ink 3) Compound of ink formula (9) (solid conversion) 2.0 parts 0.1 parts 0.025 parts water + caustic soda 78.9 parts 80.8 parts 80.875 parts Glycerin 5.0 Part 5.0 part 5.0 part urea 5.0 part 5.0 part 5.0 part N-methyl-2-pyrrolidone 4.0 part 4.0 part 4.0 part IPA 3.0 part 3.0 part 3.0 parts butyl carbitol 2.0 parts 2.0 parts 2.0 parts Surfinol 104PG50 0.1 part 0.1 part 0.1 part (surfactant manufactured by Nissin Chemical)
Total 100.0 parts 100.0 parts 100.0 parts

(B) Inkjet printing Using an inkjet printer (trade name: iP4100 manufactured by Canon Inc.), plain paper, coated paper (high-quality exclusive paper HR-101: manufactured by Canon Inc.), glossy paper (photo paper <gloss> KA450PSK: Epson Corporation) Inkjet recording was performed on three types of recording materials. Tables 4 and 5 show the results of reading the recorded image, water resistance, and moisture resistance of the ink of the present invention.

 As a comparison object, C.C. I. Direct yellow 87 (KS Light Yellow F8G: manufactured by Nippon Kayaku Co., Ltd.) was desalted with a reverse osmosis membrane to reduce the inorganic content, and 2.0 was obtained in the same manner as the compound of formula (9). Two types of inks were produced, part (Comparative Example A) and 0.1 part (Comparative Example B). The maximum absorption wavelength is λmax: 373.5 nm.

(C) Evaluation of recorded image Printing evaluation Reading of recorded images was evaluated visually. When it was difficult to judge visually, two types of wavelengths of 254 nm or 365 nm were irradiated using Hundy UV LAMP SLUV-4 (manufactured by Iuchi Seieido Co., Ltd.), and light emission was confirmed visually.
In addition, printing was performed in two types, a solid gradation pattern and a character print pattern, and evaluated visually.
A: Readable (can be distinguished)
B: Cannot be read (cannot be determined)

2. The test piece of the water resistance test recorded image was immersed in a 2-liter beaker (added with 1.5 liters of ion-exchanged water), and the color fading was visually evaluated in three stages.
○: no blur is observed Δ: blur is observed ×: large blur is observed

3. Moisture resistance test Specimens printed on coated paper and glossy paper are allowed to stand for 72 hours at 50 ° C and 90% RH using a thermo-hygrostat (manufactured by Applied Giken Sangyo Co., Ltd.), and the bleeding (bleeding) before and after the test is visually observed And evaluated in three stages.
○: no blur is observed Δ: blur is observed ×: large blur is observed

Table 3
Visual reading 254 nm irradiation 365 nm irradiation 1) Ink
Plain paper A A A
Coated paper A A A
Glossy paper A A A
2) Ink plain paper B A A
Coated paper B A A
Glossy paper B A A
3) Ink
Plain paper B A A
Coated paper B A A
Glossy paper B A A
Comparative Example A
Plain paper A A A
Coated paper A A A
Glossy paper A A A
Comparative Example B
Plain paper A A A
Coated paper A A A
Glossy paper A A A

From Table 3, the ink using the compound of the present invention has a hue that can be visually confirmed when used at a concentration of 2%, and when used at a reduced concentration of 0.1%. Characters cannot be read visually, and characters can be read by fluorescence emission by irradiating ultraviolet light of 254 nm or 365 nm. Therefore, the usage application as the anti-counterfeit ink using fluorescence is wide. On the other hand, the ink of the comparative example can sufficiently read characters visually even when the concentration is low, and its usage as a fluorescent ink is limited.

Table 4
Water resistance Moisture resistance 1) Ink
Plain paper ○ −
Coated paper ○ ○
Glossy paper ○ ○
2) Ink
Plain paper ○ −
Coated paper ○ ○
Glossy paper ○ ○
3) Ink
Plain paper ○ −
Coated paper ○ ○
Glossy paper ○ ○
Comparative Example A
Plain paper ○ −
Coated paper ○ ○
Glossy paper ○ ○
Comparative Example B
Plain paper ○ −
Coated paper ○ ○
Glossy paper ○ ○

From the results shown in Table 4, the compound of the present invention has the same level of water resistance as the comparative compound (CI Direct Yellow 87), which is known to be extremely excellent in water resistance as a water-soluble dye having fluorescence. It turns out that it has moisture resistance.

Next, 2 drops of ink, 3) ink, and Comparative Example B were dropped on a corrugated cardboard with a dropper and then stretched thinly with a brush to create a solid pattern. After drying, the reading of the stretched solid pattern was visually evaluated. When it was difficult to judge visually, two types of wavelengths of 254 nm or 365 nm were irradiated using Hundy UV LAMP SLUV-4 (manufactured by Iuchi Seieido Co., Ltd.), and light emission was confirmed visually. The results are shown in Table 5.

Table 5
Visual reading 254 nm irradiation 365 nm irradiation 2) Ink corrugated paper B A A
3) Ink
Corrugated paper B A A
Comparative Example B
Corrugated paper A A A

From Table 5, 1) ink and 2) ink using the compound of the present invention cannot be read with a solid pattern by visual observation, and a solid pattern can be read with fluorescence emission by irradiating ultraviolet light of 254 nm or 365 nm. On the other hand, the ink of Comparative Example B can be sufficiently read visually, and it is difficult to use it as an anti-counterfeit ink even on cardboard paper.

Example 3 (Fluorescence intensity measurement)
The compound (9) of the present invention was diluted 100000 times with ion-exchanged water to prepare a measurement sample, and fluorescence intensity was measured (FIG. 1: solid line, maximum fluorescence wavelength 455 nm when measured at an excitation wavelength of 379 nm). ). As a comparative example, C.I. I. Direct yellow 87 was adjusted at the same dilution factor, and fluorescence intensity was measured (FIG. 1: dotted line, maximum fluorescence wavelength 459 nm when measured at excitation wavelength 378 nm). This test was conducted with concentration quenching taken into account.

From the result of FIG. 1, the compound of the present invention has extremely high fluorescence intensity as compared with the compound of the comparative example.

From the above, the ink using the compound of the present invention is a very excellent fluorescent ink having a wide range of applications such as anti-counterfeiting.

FIG. 1 shows compound (9) (solid line) and C.I. I. The fluorescence intensity of direct yellow 87 (dotted line) was measured.

Claims (12)

A compound represented by the following formula (1) in the form of a free acid

(In formula (1), m and n each independently represent 1 or 2.) The compound represented by formula (1) according to claim 1, wherein the content of anions of Cl ^- and SO ₄ ^2- is 1% by mass or less. An ink containing the compound according to claim 1 or 2. The ink according to claim 3, comprising water and a water-soluble organic solvent. The ink according to claim 3 or 4, which is for inkjet recording. 6. An ink jet recording method for recording on a recording material by ejecting ink droplets according to a recording signal, wherein the ink according to any one of claims 3 to 5 is used. The inkjet recording method according to claim 6, wherein the recording material is an information transmission sheet. 8. The inkjet recording method according to claim 7, wherein the information transmission sheet is a surface-treated sheet having an ink image-receiving layer containing white inorganic pigment particles on a support. A container containing the ink according to any one of claims 3 to 5. An ink jet printer having the container according to claim 9. A colored body colored with the ink according to any one of claims 3 to 5. A process for producing the compound according to claim 1.

Images