KR20050023352A - Ink - Google Patents

Abstract

(a) a metal chelate compound of formula 1 or a salt thereof, wherein M is nickel; And (b) an ink comprising a liquid medium:

The ink is useful for ink jet printers.

Description

Ink {Ink}

The present invention relates to ink and its use in ink jet printing ("IJP"). IJP is a type of non-contact printing technique wherein ink droplets are ejected onto a substrate through a fine nozzle and the nozzle is not in contact with the substrate.

There are many required performance requirements for inks to be used in IJP. For example, the ink preferably provides a clear, non-feathered image with good water-fastness, daylight fastness and optical density. Ink is often required to dry quickly to prevent smudging when applied on a substrate, but no crust should be formed on the line of ink jet nozzles. This is because the printer stops working. The ink should also be storage stable over long periods of time without forming decomposition or deposits that would block the fine nozzles.

WO 01/48090 relates to metal chelate azo compounds comprising a naphthol component and certain heterocyclic groups. WO 01/48090 does not disclose that such compounds are further substituted by triazole rings for use in ink compositions.

According to a first aspect of the invention, there is provided a chemical composition comprising: (a) a metal chelate compound of formula 1 or a salt thereof, wherein M is nickel; And (b) an ink comprising a liquid medium:

The ink containing the compound of Formula 1 is particularly preferably magenta in color.

Inks comprising the compound of Formula 1 provide a print that exhibits high daylight fastness, good fastness to oxidizing gases such as ozone and especially optical density when used in ink jet printing. The ink according to the invention is also highly soluble, thereby improving workability and reducing crusting and nozzle clogging when the ink containing the compound is used in an ink jet printer.

The compound of formula 1 is particularly preferably in the form of sodium, lithium, potassium, ammonium or substituted ammonium salts. This is because these salts have been found to provide a print that exhibits high daylight fastness when incorporated into ink jet printing inks.

The metal chelate compound of Formula 1 or a salt thereof according to the present invention and an ink comprising the compound of Formula 1 also include their tautomers, in particular the tautomers of the triazole ring.

The compound of Formula 1 may be converted to a salt using known techniques. For example, the alkali metal salt of any compound can be converted to ammonia or amine salt by dissolving the alkali metal salt of the dye in water and passing the solution through a column of suitably modified ion exchange resins.

The ink according to the invention can preferably be purified to remove undesirable impurities before incorporation into the ink for ink jet printing. Conventional techniques can be used for purification. Examples are ultrafiltration, reverse osmosis and / or dialysis.

The liquid medium preferably comprises (i) water; (ii) a mixture of water and organic solvent; Or (iii) an organic solvent free of water.

The weight part of component (a) of the ink is preferably 0.01 to 30 parts, more preferably 0.1 to 20 parts, in particular 0.5 to 15 parts, and more particularly 1 to 5 parts. The weight part of component (b) is preferably 99.99 to 70 parts, more preferably 99.9 to 80 parts, in particular 99.5 to 85 parts, and more particularly 99 to 95 parts. The number of parts of (a) + (b) is 100 and all "parts" mentioned herein are parts by weight.

Preferably component (a) is completely dissolved in component (b). Preferably component (a) has a solubility of at least 10% in component (b) at 20 ° C. This makes it possible to produce concentrates which can be used to prepare more diluted inks and which can reduce the probability of precipitation of the compound of the ink component (a) if the liquid medium evaporates during storage.

When the liquid medium comprises a mixture of water and organic solvent, the weight ratio of water to organic solvent is preferably 99: 1 to 1:99, more preferably 99: 1 to 50:50 and especially 95: 5 To 80:20.

The organic solvent present in the mixture of water and organic solvent is preferably an organic solvent or a mixture of such solvents that can be mixed with water. Organic solvents which can be mixed in the preferred water are C _1-6 alkanols, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentane Ol and cyclohexanol; Linear amides, preferably dimethylformamide or dimethylacetamide; Ketones and ketone-alcohols, preferably acetone, methyl ether ketone, cyclohexanone and diacetone alcohol; Ethers which can be mixed with water, preferably tetrahydrofuran and dioxane; Diols, preferably diols having 2 to 12 carbon atoms, for example pentane-1,5-diol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol and thiodiglycol and oligo- And poly-alkylene glycols, preferably diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol; Triols, preferably glycerol and 1,2,6-hexanetriol; Diols -C _1-4 mono-alkyl ether, preferably 2-diol mono -C _1-4 of having to 12 carbon atoms-alkyl ether, especially 2-methoxyethanol, 2- (2-methoxyethoxy ) Ethanol, 2- (2-ethoxyethoxy) ethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol, 2- [2- (2-ethoxyethoxy) ethoxy] ethanol And ethylene glycol monoallyl ether; Cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; Cyclic esters, preferably caprolactone; Sulfoxides, preferably dimethyl sulfoxide and sulfolane. Preferably the liquid medium comprises an organic solvent which is mixed with water and at least two, in particular two to eight, water.

Organic solvents which can be mixed with particularly preferred water are cyclic amides, in particular 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone; Diols, in particular pentane-1,5-diol, ethylene glycol, thiodiglycol, diethylene glycol and triethylene glycol; And mono-C _1-4 -alkyl and mono-C _1-4 -alkyl ethers of diols, more preferably mono-C _1-4 -alkyl ethers of diols having 2 to 12 carbon atoms, in particular 2-methoxy -2-ethoxy-2-ethoxyethanol.

If the liquid medium comprises an organic solvent free of water (ie less than 1% by weight of water), the solvent preferably has a boiling point of 30 to 200 ° C., more preferably of 40 to 150 ° C., in particular 50 to It has a boiling point of 125 ° C. The organic solvent may be a mixture of such solvents or mixed with water, which is not mixed with water. Preferred organic solvents to be mixed with water are any of the organic solvents which can be mixed with water described above or mixtures thereof. Solvents that are not mixed with the preferred water include, for example, aliphatic hydrocarbons; Esters, preferably ethyl acetate; Chlorinated hydrocarbons, in particular CH ₂ Cl ₂ ; And ethers, preferably diethyl ether; And mixtures thereof.

When the liquid medium comprises an organic solvent which is not mixed with water, a polar solvent is preferably included since it increases the solubility of the metal chelate compound in the liquid medium. Examples of polar solvents include C _{1-4 -alcohols} . Given the above preferences, when the liquid medium is an organic solvent without water, the liquid medium comprises ketones (especially methyl ethyl ketone) and / or alcohols (especially C _1-4 -alkanols such as ethanol or propanol) Is particularly preferred.

The water free organic solvent may be a single organic solvent or a mixture of two or more organic solvents. If the medium is an organic solvent free of water, the medium is preferably a mixture of two to five different organic solvents. This allows the medium to be selected so that the drying characteristics and storage stability of the ink are well controlled.

Ink media comprising water-free organic solvents are particularly useful when printing on hydrophobic and non-absorbent substrates, such as plastics, metals and glass, especially when fast drying speeds are required.

Particularly preferred inks include (i) from 1 to 10 parts by weight of the compound of formula 1 or a salt thereof; (ii) 2 to 60 parts by weight, more preferably 5 to 40 parts by weight of a water-soluble organic solvent; And (iii) 30 to 97 parts by weight of water, more preferably 40 to 85 parts by weight, wherein the sum of the parts by weight of (i), (ii), and (iii) (i) + (ii) + (iii) ) = 100.

The liquid medium in the ink is a mixture of water and an organic solvent; Or component (i) of the ink when incorporating an organic solvent free of water may comprise a compound of formula (1) or a salt thereof as defined above.

Preferred low melting solid media have a melting point in the range of 60 ° C to 125 ° C. Suitable low melting solids include long chain fatty acids or alcohols, preferably fatty acids or alcohols having a C _18-24 chain, and sulfonamides. The compound of formula 1 may be dissolved in a low melting solid or finely dispersed in the solid.

The ink according to the invention also contains additional components commonly used in ink jet printing inks, such as viscosity modifiers, surface tension modifiers, preservatives, biocides, kogation reducing additives, paper Anti-cockle agents to reduce drying, and ionic or nonionic surfactants.

The pH of the ink is preferably 4 to 11, more preferably 7 to 10.

The viscosity at 25 ° C. of the ink is preferably less than 50 cP, more preferably less than 20 cP and especially less than 5 cP.

A second aspect of the present invention provides a process for printing an image on a substrate comprising applying an ink according to the first aspect of the invention on an substrate by an ink jet printer. Preferred inks used in the process are the inks defined above in connection with the first aspect of the invention.

Ink jet printers apply ink onto a substrate, preferably in the form of droplets ejected through small holes. Preferred ink jet printers are piezoelectric ink jet printers or thermal ink jet printers. In the case of a thermal ink jet printer, a programmed thermal pulse is applied to the ink in the reservoir by a resistor adjacent to the aperture, causing ink to be ejected toward the substrate in the form of droplets during the relative movement between the substrate and the aperture. In the case of piezoelectric ink jet printers, oscillation of small crystals causes ink to be ejected from the holes.

The substrate is preferably paper, plastic, fiber, metal or glass, more preferably paper, overhead projector slide or fibrous material, in particular paper.

Preferred papers are plain paper or treated paper, which may have acidic, alkaline or neutral properties. Examples of commercially available papers include HP Premium Coated Paper, HP Photopaper (all available from Hewlett Packard Inc.), Stylus Pro 720dpi Coated Paper, Epson Phto Quality Glossy Film, Epson Phto Quality Glossy Paper (Seiko Epson Corp. Available from Canon HR 101 High Resolution Paper, Canon GP 201 Glossy Paper, Canon HG 101 High Gloss Film (all available from Canon Inc.), Wiggins Conqueror paper (available from Wigsgin Teape Ltd.), Xerox Acid Paper and Xerox Alkaline paper, Xerox Acid Paper (available from Xerox).

A third aspect of the invention provides a substrate, preferably paper, overhead projector slides, or fibrous material, which is printed with ink according to the first aspect of the invention or subjected to a process according to the second aspect of the invention. Is printed.

According to a fourth aspect of the present invention, there is provided an ink jet printer cartridge comprising a chamber and ink, the ink being in the chamber and the ink as defined in the first aspect of the present invention.

According to a fifth aspect of the invention, there is provided an ink jet printer comprising the ink jet printer cartridge, wherein the ink jet printer cartridge is as defined in the fourth aspect of the invention.

The invention is illustrated in more detail by the following examples. In the following all "parts" and "%" refer to "parts by weight" and "% by weight" unless otherwise defined.

 Example 1

 Compound 1 where M is nickel

Stage (a): Synthesis of 2-acetoxynaphthalene-3,6-disulfonic acid

Acetic anhydride (350 ml, 3.8 mol) was added dropwise to a suspension of 2-hydroxynaphthalene-3,6-disulfonic acid disodium salt (87 g, 0.25 mol) in N, N-dimethylacetamide (350 ml). . The reaction mixture was stirred at 125 ° C. for 24 hours, cooled to room temperature and added to acetone (2500 ml). The product was filtered off, washed with acetone (3 x 100 ml) and dried to give 95.2 g of a cream solid.

Stage (b): 3,6-bis- (4-carboxy-phenylsulfamoyl) -2-hydroxy-naphthalene

POCl ₃ (50 ml, 0.538 mol) was added dropwise at reflux to a suspension of the product of stage (a) (50 g, 0.128 mol) in acetonitrile (250 ml). The reaction mixture was stirred at 70 ° C. for 3 hours, cooled, added to ice / water (4000 ml) and naphthalene disulfonyl chloride was extracted with dichloromethane (4 × 300 ml). The combined extracts were dried over MgSO ₄ , evaporated under reduced pressure and the residue was dissolved in N, N-dimethylacetamide (400 ml). 4-Aminobenzoic acid (34.3 g, 0.25 mol) was added to the solution, and the reaction mixture was stirred overnight at room temperature and added to water (3000 ml). The pH was then lowered to 0.5 with concentrated H ₂ S0 ₄ and the precipitated product was extracted with ethyl acetate (4 x 300 ml). The extract was washed with 1N HCl (600 ml), dried over MgSO ₄ and evaporated under reduced pressure. The residue was dissolved in water (1000 ml) at pH 12 (2N NaOH) and stirred at 50-60 ° C. for 1 hour. The solution was cooled and the pH was lowered to pH 4 with concentrated HCl and the product was filtered and dried to give 41.5 g (53% yield) of a tan solid.

Stage (c)

3-amino-1,2,4-triazole-5-carboxylic acid hydrate (1.28 g, 0.01 mol) was suspended in water (50 ml) and dissolved at pH 8 by addition of 2M NaOH. Sodium nitrite (0.76 g, 0.011 mol) was added and the solution stirred until sodium nitrite dissolved.

The mixture was added dropwise to a cooled mixture of ice-water (30 g) and concentrated HCl (3.0 ml) at 0-5 ° C. and the mixture was stirred at 0-5 ° C. for 30 minutes, followed by excess of nitrous acid. Sulfamic acid was added to remove. The diazo suspension was slowly added to a solution of the product of stage (b) (5.42 g, 0.01 mol) in water (100 ml) cooled to 5 ° C. or below at pH 7-8 (2N NaOH). The reaction mixture was then stirred for an additional hour at 0-5 ° C. and the product was precipitated by acidifying to pH 4 with 2N HCl and collected by filtration. The product was then washed with water and dried in a vacuum desiccator to yield 6.4 g of an orange solid.

Stage (d): Preparation of Compound 1

A solution of nickel acetate tetrahydrate (1.38 g, 0.0055 mol) in water (10 ml) was added dropwise to the product of stage (c) (5.0 g, 0.0073 mol) dissolved in water (100 ml) at pH 7 (2N NaOH). The reaction mixture was stirred at ambient temperature for 2 hours and dialyzed to low conductivity (<100 kPa) using SpextraPor membrane tubing (molecular weight cutoff 3500). This product was evaporated under reduced pressure to give a dark crystalline solid (6 g). Analysis using mass spectroscopy revealed m / z 1419. Theoretical value M ⁺ = 1420.

 Example 2-Ink

The inks described in Tables 1 and 2 can be prepared. The compound described in the first column here is the compound prepared in Example 1. The numbers listed after the second column represent parts by weight of the component. This ink may be applied to the paper by thermal or piezoelectric ink jet printing.

In Tables 1 and 2 the following abbreviations are used:

PG = propylene glycol

DEG = diethylene glycol

NMP = N-methyl pyrrolidone

DMK = dimethyl ketone

IPA = Isopropanol

MeOH = Methanol

2P = 2-pyrrolidone

MIBK = methyl isobutyl ketone

P12 = propane-1,2-diol

BDL = butane-2,3-diol

CET = cetyl ammonium bromide

PHO = Na ₂ HPO ₄

TBT = tertiary butanol

TDG = thiodiglycol.

compound Dye content water PG DEG NMP DMK NaOH Na stearate IPA MeOH 2P MIBK One 2.0 80 5 6 4 5 One 3.0 90 5 5 0.2 One 10.0 85 3 3 3 5 One One 2.1 91 8 One One 3.1 86 5 0.2 4 5 One 1.1 81 9 0.5 0.5 9 One 2.5 60 4 15 3 3 6 10 5 4 One 5 65 20 10 One 2.4 75 5 4 5 6 5 One 4.1 80 3 5 2 10 0.3 One 3.2 65 5 4 6 5 4 6 5 One 5.1 96 4 One 10.8 90 5 5 One 10.0 80 2 6 2 5 One 4 One 1.8 80 5 15 One 2.6 84 11 5 One 3.3 80 2 10 2 6 One 12.0 90 7 0.3 3 One 5.4 69 2 20 2 One 3 3 One 6.0 91 4 5

compound Dye Ingredient water PG DEG NMP CET TBT TDG BDL PHO 2P PI2 One 3.0 80 15 0.2 5 One 9.0 90 5 1.2 5 One 1.5 85 5 5 0.15 5.0 0.2 One 2.5 90 6 4 0.12 One 3.1 82 4 8 0.3 6 One 0.9 85 10 5 0.2 One 8.0 90 5 5 0.3 One 4.0 70 10 4 One 4 11 One 2.2 75 4 10 3 2 6 One 10.0 91 6 3 One 9.0 76 9 7 3.0 0.95 5 One 5.0 78 5 11 6 One 5.4 86 7 7 One 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5 One 2.0 90 10 One 2 88 10 One 5 78 5 12 5 One 8 70 2 8 15 5 One 10 80 8 12 One 10 80 10

As described above, the ink according to the present invention is useful for an ink jet printer.

Claims (8)

(a) a metal chelate compound of formula 1 or a salt thereof, wherein M is nickel; And (b) an ink comprising a liquid medium: . The ink of claim 1 wherein the liquid medium comprises a mixture of water and an organic solvent. According to claim 1 or 2, (i) 1 to 10 parts by weight of the compound of Formula 1 or a salt thereof; (ii) 2 to 60 parts by weight of a water-soluble organic solvent; And (iii) 30 to 97 parts by weight of water, (i) + (ii) + (iii) = 100 parts by weight of ink. A process of printing an image on a substrate comprising the step of applying the ink according to any one of claims 1 to 3 by an ink jet printer. A substrate printed with the ink according to any one of claims 1 to 3 or printed by the process according to claim 4. An ink jet printer cartridge comprising a chamber and ink, wherein the ink is present in the chamber and the ink is the ink according to any one of claims 1 to 3. An ink jet printer comprising an ink jet printer cartridge, wherein the ink jet printer cartridge is an ink jet printer cartridge according to claim 6. Inks substantially described in connection with any of the embodiments.