Patent Grant
8419849
This application is a 371 filing based on PCT/GB2009/051333, filed Oct. 8, 2009, which claims priority to United Kingdom Application No. 0818568.8, filed Oct. 10, 2008 all of which are hereby incorporated by reference in their entirety.
This invention relates to compounds, compositions and inks, to printing processes, to printed materials and to ink-jet printer cartridges.
Ink-jet printing is a non-impact printing technique in which droplets of ink are ejected through a fine nozzle onto a substrate without bringing the nozzle into contact with the substrate. The set of inks used in this technique typically comprise yellow, magenta, cyan and black inks.
With the advent of high-resolution digital cameras and ink-jet printers it is becoming increasingly common for consumers to print photographs using an ink-jet printer.
While ink-jet printers have many advantages over other forms of printing and image development there are still technical challenges to be addressed. For example, there are the contradictory requirements of providing ink colorants that are soluble in the ink medium and yet display excellent wet-fastness (i.e. prints do not run or smudge when exposed to water). The inks also need to dry quickly to avoid sheets sticking together after they have been printed, but they should not crust over the tiny nozzles used in the printer. Storage stability is also important to avoid particle formation that could block the print-head nozzles especially since consumers can keep an ink-jet ink cartridge for several months. Furthermore, and especially important with photographic quality reproductions, the resultant images should not fade rapidly on exposure to light or atmospheric oxidising gases such as ozone. It is also desirable that the shade and chroma of the colorant are within a narrow tolerance so that an image may be optimally reproduced.
Thus, developing new colorants for ink-jet printing presents a unique challenge in balancing all these conflicting and demanding properties.
The present invention aims to provide colorants especially suited for use in ink jet printing inks which are improved in respect of one or more of the above properties.
According to a first aspect of the present invention there is provided a compound of Formula (1) or a salt thereof:
wherein:
Preferably Z is optionally substituted C1-12-alkyl (especially optionally substituted C1-4-alkyl), optionally substituted phenyl or optionally substituted naphthyl. It is particularly preferred that Z is optionally substituted naphthyl.
We have found that Compounds of Formula (1) and salts thereof wherein Z is optionally substituted naphthyl tend to have even better overall properties for ink jet printing.
In particular we have found these (z=naphthyl) compounds tend to provide prints having even better light and/or ozone fastness. Whilst not wishing to be limited by theory we speculate that the combination of:
When Z is optionally substituted naphthyl the naphthyl is preferably attached in the 2-position.
Preferably, Z is an unsubstituted naphthyl group.
Optional substituents for Z
Optional substituents which may be present on Z are preferably selected from:
When Z is aryl, aryloxy or heterocyclyl it may also carry optionally substituted alkyl (especially C1-4-alkyl) substituents.
When present the optional substituents on the optionally substituted alkoxy, aryl, aryloxy, heterocyclyl and alkyl groups (as motioned above in respect of the Z group) may be selected from halo, amino, nitro, cyan(O) hydroxy, sulfonic acid, carboxylic acid and phosphonic acid groups.
When present, halo is preferably Cl, Br or F.
Preferred optional substituents for Z are water solubilising groups particularly carboxy (especially carboxylic acid), sulfo (especially sulfonic acid) and phosphato (especially phosphonic acid) and more especially carboxy and sulfo.
Ar
Preferably Ar is phenyl or more preferably naphthyl. (The substituents possible being as hereinbefore described).
More preferably Ar is naphthyl carrying at least one of the compulsory substituents and optionally at least one further substituent.
When Ar is naphthyl it is preferably attached in the 2-position.
Compulsory Substituents on Ar
It will be appreciated that the Ar group must compulsorily carry at least one substituent selected from the group consisting of an acetyl group, an acetate ester group, an amide group, a sulfonamide group, a sulfoxide group, a sulfone group, a phosphonate group, a nitrile group, an isonitrile group, a quaternary amine, a carbonyl group (other than a carboxylic acid), a polyhaloalkyl group or a halogen atom. We have found that these electron withdrawing groups tend to improve the light and/or ozone fastness of the compounds of Formula (1) and salts thereof.
If present the polyhalo alkyl group is preferably —CF3.
If present the halogen atom is preferably Cl, Br or F.
Preferably, at least one of the compulsory substituent groups on Ar is selected from nitrile (—CN), sulfone and sulfonamide substituents.
Preferably, at least one of the compulsory substituents on Ar is selected from —CN, —SO2R1 and especially —SO2NR2R3 substituents wherein R1 is optionally substituted alkyl, optionally substituted aryl or optionally substituted heterocyclyl and R2 and R3 are independently H, optionally substituted alkyl, optionally substituted aryl or optionally substituted heterocyclyl
Preferably, R1 is optionally substituted C1-4-alkyl, optionally substituted phenyl or optionally substituted naphthyl.
It is particularly preferred that R1 is: C1-4-alkyl carrying one or more water solubilising groups selected from the group consisting of carboxy (especially carboxylic acid), sulfo (especially sulfonic acid) and phosphato (especially phosphonic acid) and especially carboxy and sulfo; optionally substituted phenyl carrying one or more water solubilising groups selected from the group consisting of carboxy (especially carboxylic acid), sulfo (especially sulfonic acid) and phosphato (especially phosphonic acid) and especially carboxy and sulfo; or optionally substituted naphthyl carrying one or more water solubilising groups selected from the group consisting of carboxy (especially carboxylic acid), sulfo (especially sulfonic acid) and phosphato (especially phosphonic acid) and especially carboxy and sulfo.
R2 and R3 are preferably selected from the group consisting of H; an aryl group carrying one or more water solubilising groups selected from the group consisting of carboxy (especially carboxylic acid), sulfo (especially sulfonic acid) and phosphato (especially phosphonic acid) and especially carboxy and sulfo; and C1-4-alkyl carrying one or more water solubilising groups selected from the group consisting of carboxy (especially carboxylic acid), sulfo (especially sulfonic acid) and phosphato (especially phosphonic acid) and especially carboxy and sulfo.
More especially, it is preferred that one of R2 and R3 is H and the other is:
Even more preferably, at least one of the compulsory substituent on Ar is a naphthyl sulphonamide of the formula —SO2NR2R3 wherein R2 is napthyl which is substituted with from 1 to 3 groups selected from sulfonic acid, carboxylic acid and phosphonic acid groups and R3 is H. Preferably Ar carries from 1 to 3 and especially 1 or 2 of the above mentioned naphthyl sulfonamide substituents.
It is particularly preferred that the naphthyl sulphonamide is of the Formulae:
Optional Further Substituents on Ar
It will be appreciated that the further substituents are other than those mentioned as compulsory substituents.
Optionally, Ar is not substituted with any nitro groups.
When present the optional further substituent on Ar is preferably selected from:
optionally substituted alkyl;
optionally substituted alkoxy,
optionally substituted aryl,
optionally substituted aryloxy,
optionally substituted heterocyclyl,
polyalkylene oxide, sulfonic acid, carboxylic acid, hydroxy and nitro groups.
When present the optional substituents on the optionally further substituted alkyl, alkoxy, aryl, aryloxy and heterocyclyl (as motioned above in respect of the Ar group) may be selected from halo, amino, nitro, cyano, hydroxy, sulfonic acid, carboxylic acid and phosphonic acid groups.
Preferably, Ar is not substituted with electron donating groups such as alkyl, aryl or heterocyclyl groups. Preferably, Ar only carries groups selected from the compulsory list of substituents which are electron withdrawing.
Preferably, from 1 to 3 water solubilising groups are directly or indirectly attached to Ar. The preferred water solubilising groups are carboxy (especially carboxylic acid), phosphato (especially phosphonic acid) and more preferably sulfo (especially sulfonic acid).
General Preferences for Substituents
When Z, R1, R2 and R3 are optionally substituted alkyl they may, be linear, branched or cyclic alkyl groups. When R1, R2 and R3 are optionally substituted alkyl preferably they are optionally substituted C1-12 alkyl, and more preferably optionally substituted C1-4 alkyl.
When R1, R2 and R3 are optionally substituted aryl they are preferably optionally substituted phenyl or naphthyl.
When Z, R1, R2 and R3 are optionally substituted heterocyclyl they are preferably a 5- or 6-membered ring containing N and optionally 1 or more other heteroatoms.
Fibre Reactive Croups
The compounds of Formula (1) or a salts thereof are also preferably free from fibre reactive groups. The term fibre reactive group is well known in the art and is described for example in EP 0356014 A1. Fibre reactive groups are capable, under suitable conditions, of reacting with the hydroxyl groups present in cellulosic fibres or with the amino groups present in natural fibres to form a covalent linkage between the fibre and the dye. As examples of fibre reactive groups excluded from the compounds of Formula (1) there may be mentioned aliphatic sulfonyl groups which contain a sulfate ester group in beta-position to the sulfur atom, e.g. beta-sulfato-ethylsulfonyl groups, alpha, beta-unsaturated acyl radicals of aliphatic carboxylic acids, for example acrylic acid, alpha-chloro-acrylic acid, alpha-bromoacrylic acid, propiolic acid, maleic acid and mono- and dichloro maleic; also the acyl radicals of acids which contain a substituent which reacts with cellulose in the presence of an alkali, e.g. the radical of a halogenated aliphatic acid such as chloroacetic acid, beta-chloro and beta-bromopropionic acids and alpha, beta-dichloro- and dibromopropionic acids or radicals of vinylsulfonyl- or beta-chloroethylsulfonyl- or beta-sulfatoethyl-sulfonyl-endo-methylene cyclohexane carboxylic acids. Other examples of cellulose reactive groups are tetrafluorocyclobutyl carbonyl, trifluoro-cyclobutenyl carbonyl, tetrafluorocyclobutylethenyl carbonyl, trifluoro-cyclobutenylethenyl carbonyl; activated halogenated 1,3-dicyanobenzene radicals; and heterocyclic radicals which contain 1, 2 or 3 nitrogen atoms in the heterocyclic ring and at least one cellulose reactive substituent on a carbon atom of the ring, for example a triazinyl halide.
It will be appreciated that all of above mentioned preferred substituents are not fibre reactive groups.
Salts
When acid or basic groups (particularly acid groups) are present in the compounds of Formula (1) they are preferably in the form of a salt. Thus, all Formulae shown herein include the compounds in salt form.
Preferred salts are alkali metal salts, especially lithium, sodium and potassium, ammonium and substituted ammonium salts (including quaternary amines such as ((CH3)4N+) and mixtures thereof. Especially preferred are salts with sodium, lithium, ammonia and volatile amines, more especially lithium and sodium salts. Compounds of Formula (1) where lithium is the major salt form are especially preferred. Preferably, the compounds of Formula (1) is in the form of a lithium salt.
Compounds of Formula (1) may be converted into a salt using known techniques.
The compounds of Formula (1) and salts thereof may exist in tautomeric forms other than those shown in this specification. These tautomers are included within the scope of the present invention and its claims.
Preferred Compounds of Formula (1)
Preferred compounds of Formula (1) and salts thereof are of the Formulae (2) to (4) and salts thereof:
The above compounds of Formulae (2) to (4) have been found to display, among other things, especially good light fastness.
Preferably, the compounds of Formulae (2) to (4) or a salt thereof are in the form of the lithium salt.
Other compounds of Formula (1) or salts thereof include those of Formulae (5) to (10) and salts thereof:
Synthesis
The compounds of Formula (1) and salts thereof may be prepared by any method known in the art, and particularly by processes such as those described in U.S. Pat. No. 7,192,475 which is incorporated herein by reference.
The compounds of Formula (1) or salts thereof described herein can be synthesised by methods known in the art. For example, an aryl amine may be diazotised under aqueous conditions with sodium nitrite and hydrochloric acid. The diazotised aryl amine may then be added to a solution or suspension of a cyano substituted thiophene amine or a thiazole amine. Sometimes, a miscible organic solvent such as methanol or N-methyl-2-pyrrolidone can be used as a cosolvent in conjunction with water. The resulting monoazo compound, once isolated, can be reacted with a pyridine-based coupler in a manner that ensures diazotisation and coupling occur in situ. For this coupling step it may be advantageous to use for example isoamyl nitrite.
Alternatively, a step-wise synthetic method can be used, for example the monoazo compound may be diazotised prior to the coupling reaction.
One suitable synthetic method is described schematically as indicated below:
wherein Ar, X and Z are as hereinbefore defined.
The compounds of Formula (1) and salt thereof are valuable colorants for use in the preparation of ink-jet printing, especially black, inks. They benefit from a good balance of solubility, storage stability and fastness to water, ozone and light. In particular they display excellent light fastness.
Compositions and Inks
According to a second aspect of the present invention there is provided a composition comprising a compound of Formula (1) or a salt thereof according to the first aspect of the invention and a liquid medium.
Preferred compositions according to the second aspect of the invention comprise:
Preferably, the number of parts of (a)+(b)=100.
The number of parts of component (a) is preferably from 0.1 to 20, more preferably from 0.5 to 15, and especially from 1 to 5 parts. The number of parts of component (b) is preferably from 80 to 99.9, more preferably from 85 to 99.5 and especially from 95 to 99 parts.
Preferably component (a) is completely dissolved in component (b). Preferably component (a) has a solubility in component (b) at 20° C. of at least 1% by weight, more preferably at least 2%, especially at least 5% and most especially at least 10% by weight. This allows the preparation of liquid dye concentrates that may be used to prepare more dilute inks and reduces the chance of the dye precipitating if evaporation of the liquid medium occurs during storage. Preferably, the liquid medium for establishing the required solubility is water.
Thus, the present invention also provides a composition (preferably an ink) where component (a) is present in an amount of 2.5 to 7 parts, more preferably 2.5 to 5 parts (a high concentration ink) or component (a) is present in an amount of 0.5 to 2.4 parts, more preferably 0.5 to 1.5 parts (a low concentration ink).
Preferred liquid media include water, a mixture of water and organic solvent and organic solvent free from water. Preferably, the liquid medium comprises a mixture of water and organic solvent or organic solvent free from water.
When the liquid medium (b) comprises a mixture of water and organic solvent, the weight ratio of water to organic solvent is preferably from 99:1 to 1:99, more preferably from 99:1 to 50:50, especially from 99:1 to 70:30 and most especially from 95:5 to 80:20.
It is preferred that the organic solvent present in the mixture of water and organic solvent is a water-miscible organic solvent or a mixture of such solvents. Preferred water-miscible organic solvents include C1-6-alkanols, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol and cyclohexanol; linear amides, preferably dimethylformamide or dimethylacetamide; ketones and ketone-alcohols, preferably acetone, methyl ether ketone, cyclohexanone and diacetone alcohol; water-miscible ethers, preferably tetrahydrofuran and dioxane; diols, preferably diols having from 2 to 12 carbon atoms, for example ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol and thiodiglycol and oligo- and poly-alkyleneglycols, preferably diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol; triols, preferably glycerol and 1,2,6-hexanetriol; mono-C1-4-alkyl ethers of diols, preferably mono-C1-4-alkyl ethers of diols having 2 to 12 carbon atoms, especially 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol, 2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol and ethyleneglycol monoallylether; 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 sulfones, preferably sulfolane. Preferably the liquid medium comprises water and 2 or more, especially from 2 to 8, water-miscible organic solvents.
Especially preferred water-miscible organic solvents are cyclic amides, especially 2-pyrrolidone, N-methyl-pyrrolidone and N-ethyl-pyrrolidone; diols, especially 1,5-pentane diol, ethyleneglycol, thiodiglycol, diethyleneglycol and triethyleneglycol; and mono-C1-4-alkyl and C1-4-alkyl ethers of diols, more preferably mono-C1-4-alkyl ethers of diols having 2 to 12 carbon atoms.
When the liquid medium comprises organic solvent free from water, (i.e. less than 1% water by weight) the solvent preferably has a boiling point of from 30 to 200° C., more preferably of from 40 to 150° C., especially from 50 to 125° C. The organic solvent may be water-immiscible, water-miscible or a mixture of such solvents. Preferred water-miscible organic solvents are any of the hereinbefore-described water-miscible organic solvents and mixtures thereof. Preferred water-immiscible solvents include, for example, aliphatic hydrocarbons; esters, preferably ethyl acetate; chlorinated hydrocarbons, preferably CH2Cl2; and ethers, preferably diethyl ether; and mixtures thereof.
When the liquid medium comprises a water-immiscible organic solvent, preferably a polar solvent is included because this enhances solubility of the mixture of dyes in the liquid medium. Examples of polar solvents include C1-4-alcohols and ketones.
In view of the foregoing preferences it is especially preferred that where the liquid medium is organic solvent free from water it comprises a ketone (especially methyl ethyl ketone) and/or an alcohol (especially a C1-4-alkanol, more especially ethanol or propanol).
The organic solvent free from water may be a single organic solvent or a mixture of two or more organic solvents. It is preferred that when the liquid medium is organic solvent free from water it is a mixture of 2 to 5 different organic solvents. This allows a liquid medium to be selected that gives good control over the drying characteristics and storage stability of the ink.
Liquid media comprising organic solvent free from water are particularly useful where fast drying times are required and particularly when printing onto hydrophobic and non-absorbent substrates, for example plastics, metal and glass.
The liquid media may of course contain additional components suitable for use in ink-jet printing inks, for example viscosity and surface tension modifiers, corrosion inhibitors, biocides, kogation reducing additives and surfactants which may be ionic or non-ionic.
Colour Blends
The compositions and inks described above may contain one compound of Formula (1) or a salt thereof or a mixture of two or more compounds of Formula (1) or salts thereof.
Optionally, further colorant(s) not of Formula (1) or a salt thereof may be added to the ink to modify the shade and performance properties. They may also be added to adjust the cost:performance ratio.
The further colorant(s) may be of any colour (including cyan, magenta, yellow and especially black). Preferably, the further colorant are themselves suitable for ink jet printing inks. Further colorants may be selected from those listed in the Colour Index, and salts thereof, and those commercially available specifically for ink-jet printing. The further colorants may be pigments but more preferably they are dyes and especially water soluble dyes.
Preferably, the further colorants are selected from those disclosed in U.S. Pat. Nos. 7,491,266, and 7,533,978, the examples of which are incorporated herein by reference.
Suitable further black colorants include C.I. Food Black 2, C.I. Direct Black 19, C.I. Reactive Black 31, PRO-JET™ Fast Black 2, C.I. Direct Black 195; C.I. Direct Black 168; and black dyes described in patents by Lexmark (e.g. EP 0539178 A2, Example 1, 2, 3, 4 and 5) and Orient Chemicals (e.g. EP 0347803 A2, pages 5-6, azo dyes 3, 4, 5, 6, 7, 8, 12, 13, 14, 15 and 16)
Suitable further magenta colorants include PRO-JET™ Fast Magenta 2.
Suitable further yellow colorants include C.I. Direct Yellow 142; C.I. Direct Yellow 132; C.I. Direct Yellow 86; C.I. Direct Yellow 85; C.I. Direct Yellow 173; and C.I. Acid Yellow 23.
Suitable further cyan colorants include phthalocyanine colorants, e.g. Direct Blue 199 and Acid Blue 99.
It will be appreciated that the compositions and inks described above may be used as the black ink in a colour printing ink set. Suitable colorants for the magenta, yellow and cyan inks in the set are well known in the arts and can be chosen readily from any of those disclosed in the art or commercially available. The further magenta, yellow and cyan colorants described above may be used to prepared the yellow, magenta and cyan inks in the ink set.
It is preferred that the composition according to the second aspect of the present invention is an ink suitable for use in an ink-jet printer. Such a composition may also be referred to herein simply as an “ink jet printer ink”. Ink suitable for use in an ink-jet printer is ink which is preferably able to repeatedly fire through an ink-jet printing head without causing blockage of the fine nozzles. To do this the ink is preferably substantially free of particles of a size of greater than 1 micron in diameter, stable (i.e. does not precipitate on storage and has a viscosity which allows for good droplet formation at the print head. For thermal ink jet printer inks it is also preferred that the composition is substantially free from metal corrosive components such as chloride ions.
Ink suitable for use in an ink-jet printer preferably has a viscosity of less than 30cP, more preferably less than 20 cP, especially less than 10 cP and most especially less than 5 cP at 25° C. 1cPs equals 1 mPa·s.
Ink suitable for use in an ink-jet printer preferably contains less than 500 ppm, more preferably less than 250 ppm, especially less than 100 ppm, more especially less than 10 ppm in total of divalent and trivalent metal ions (other than any divalent and trivalent metal ions bound to a compound of Formula (1) or any other colorant or additive incorporated in the ink).
Preferably ink suitable for use in an ink-jet printer has been filtered through a filter having a mean pore size below 10 μm, more preferably below 3 μm, especially below 2 μm, more especially below 1 μm. This filtration removes particulate matter that could otherwise block the fine nozzles found in many ink-jet printers.
Preferably, ink suitable for use in an ink-jet printer contains less than 500 ppm, more preferably less than 250 ppm, especially less than 100 ppm, more especially less than 10 ppm in total of halide ions.
Printing Process
According to a third aspect of the present invention there is provided a process for forming an image on a substrate comprising ink jet printing a composition according to the second aspect of the present invention which is suitable for use in an ink-jet printer (an ink jet printer ink) to the substrate.
The ink-jet printer preferably applies the ink to the substrate in the form of droplets that are ejected through a small orifice onto the substrate. Preferred ink-jet printers are piezoelectric ink-jet printers and thermal ink-jet printers. In thermal ink-jet printers, programmed pulses of heat are applied to the ink in a reservoir by means of a resistor adjacent to the orifice, thereby causing the ink to be ejected from the orifice in the form of small droplets directed towards the substrate during relative movement between the substrate and the orifice. In piezoelectric ink-jet printers the oscillation of a small crystal causes ejection of the ink from the orifice. Alternately, the ink can be ejected by an electromechanical actuator connected to a moveable paddle or plunger, for example as described in International Patent Application WO00/48938 and International Patent Application WO00/55089.
The substrate is preferably paper, plastic, a textile, metal or glass, more preferably paper, an overhead projector slide or a textile material, especially paper.
Preferred papers are plain or treated papers which may have an acid, alkaline or neutral character. Photographic quality papers are especially preferred. In some embodiments the paper may have an ink jet receptor coating which may be porous or swellable.
Printed Material (Substrate)
According to a fourth aspect of the present invention there is provided a material (substrate) printed with a compound or a salt thereof according to the first aspect of the present invention, a composition according to the second aspect of the invention or by means of a process according to the third aspect of the invention.
The material used is preferably paper, plastic, a textile, metal or glass, more preferably paper, an overhead projector slide or a textile material, especially paper more especially plain, coated or treated papers
It is especially preferred that the printed material of the fourth aspect of the invention is a print on a photographic quality paper printed using a process according to the third aspect of the present invention.
According to a fifth aspect of the present invention there is provided an ink-jet printer cartridge comprising a chamber and a composition according to the second aspect of the present invention which is suitable for use in an ink-jet printer, wherein the composition is in the chamber.
The invention is further illustrated by the following Examples in which all parts and percentages are by weight unless otherwise stated.
Stage 1a
2-Naphthylamine-6-sulfonic acid (Bronner acid) (supplied by TCI, 111.5 g; 0.5 mol) was stirred in water at pH 9.5 to form a solution. Acetic anhydride (76.0 g: 0.075 mol) was then added dropwise to the solution at a temperature under 25° C. to form a reaction mixture. The reaction mixture was stirred overnight at room temperature. The product was precipitated by the addition of 30% aqueous sodium chloride, collected by filtration and washed with 25% aqueous sodium chloride solution. The resultant precipitate was stirred with acetone, collected by filtration and the treatment was repeated. The resulting solid was dried in an oven to give an off white solid (144.5 g).
Stage 1b
The product of stage 1a (78.4 g: 0.20 mol) was added to stirred chlorosulfonic acid at a temperature of less than 20° C. over 1 hour and then stirred at room temperature overnight. The resulting solution was drowned into ice/water causing the product to precipitate. The precipitate was collected by filtration and washed with water. The resulting solid was dried to give an off white solid (49.10 g).
Stage 1c
2-Naphthylamine-4,6,8-trisulfonic acid (21.87 g; 0.03 mol) was dissolved in water (200 ml) at pH 7 whilst stirring. A solution of the product of stage 1b (10.599; 0.03 mol) in acetone (200 ml) was added dropwise to the naphthylamine solution at 10-13° C. over 5 minutes maintaining the pH at 7-8 by the addition of 1M aqueous sodium carbonate solution. This formed a reaction mixture. After stirring overnight the reaction mixture was filtered and the filtrate was evaporated to a reduced volume. The resulting viscous filtrate was diluted with methylated spirits 74OP and stirred for 1 hour to cause precipitation of the product. The product was collected by filtration and washed with methylated spirits 74OP. The product was dried to give a pale yellow solid (28.7 g).
Stage 1d
The product of stage 1c (28 g) was stirred in 1M HCl (110 ml) and heated at 80° C. for 2.5 hours. This formed a solution. The solution was then cooled to room temperature, diluted with methylated spirits 74OP (500 ml) and stirred for 30 minutes. This caused the product to precipitate. The precipitate was collected by filtration and washed with methylated spirits 74OP. The resulting solid was oven dried to give a fawn coloured solid (13.88 g).
Stage 1e
The intermediate of Stage 1e was prepared as described in U.S. Pat. No. 7,083,670 at column 23.
Stage 1f
The product of stage 1d (0.02 mol) was dissolved in water (200 ml) with stirring and concentrated hydrochloric acid (8 ml) was added. 1.0M sodium nitrite (21 ml; 0.021 mol) was then added drop-wise at 0-10° C. over 5 minutes to the solution containing the product of stage 1d. After stirring for 1 hour at 0-10° C. the excess nitrous acid was destroyed by the addition of sulfamic acid. The resulting solution was then added dropwise over 5 minutes to a stirred solution of the product of stage 1e (0.020 mol) in methanol (400 ml) at a temperature of less than 20° C. This formed a reaction mixture. The reaction mixture was stirred overnight at a temperature of around 25° C. The product was then precipitated by adding a 15% aqueous lithium chloride solution. The precipitate was collected by filtration and washed with 20% aqueous lithium chloride solution. The resulting precipitate was dried in an oven to give a reddish black solid 30.1 g.
Stage 1g
The product of stage 1f (0.01 mol) and a pyridine coupler (0.011 mol), (prepared as described in EP 1553147 and JP-A-2003-306623) were combined in water at 45° C. and pH 4. Isoamyl nitrite (2.69 ml:0.02 mol) was then added. The resultant mixture was stirred for 2.5 hours at 45° C., and then filtered. The filtrate was adjusted to pH 7 and the product was precipitated by adding a 35% aqueous lithium chloride solution. The precipitate was then stirred with propan-1-ol (500 ml) and propan-2-ol (1000 ml) and warmed to around 60° C. to form a mixture. The mixture was allowed to cool to a temperature of around 25° C. and the resulting solid was collected by filtration. The solid was dissolved in water (300 ml) at pH 9 and dialysed using Visking™ tubing to a conductivity of less than 30 μScm−1. The dialysed solution was then filtered (GF/F, 0.45 μm nylon) and dried in an oven to give a reddish black solid 0.71 g. The compound of Example 1 had a lambda max in water of 603 nm and an extinction coefficient of 32,800 dm3 mol−1 cm−1.
The compound of Example 2 was prepared in exactly the same way as in Example 1 except that the intermediate of stage 1e was replaced with
(0.020 mol) which was purchased from Alfa. The compound of Example 2 had a lambda max in water of 594 nm and an extinction coefficient of 38,900 dm3 cm−1.
Prepared as in Example 1 except that:
The comparative dye was the lithium salt of Example D 41 in U.S. Pat. No. 7,192,475:
Preparation of Inks
Inks were prepared by dissolving 3 parts by weight of the dye of Example 2 and the Comparative Dye in 97 parts by weight of a liquid medium comprising % by weight:
and adjusting the pH of the ink to 8-8.5 using aqueous sodium hydroxide solution.
Surfynol™ 465 is a surfactant from Air Products.
Tris buffer comprises tris(hydroxymethyl)aminomethane.
The inks were prepared and referenced according to Tablet
Ink-jet Printing
The Inks prepared as described above were filtered through a 0.45 micron nylon filter and then incorporated into empty print cartridges using a syringe.
The inks were each ink jet printed on to Canon Professional Photo Paper (PR101) and HP Advanced Photo Paper (HP APP).
Print Testing
The light fastness of the printed ink to was measured by the difference in the reflectance optical density (ROD) before and after exposure to light.
Each printed image was exposed to light in an Atlas® Ci5000 Weatherometer for 100 hours.
Reflectance optical density measurements were performed using a Gretag® spectrolino spectrophotometer set to the following parameters:
The light fastness was quantified by the percentage change in the reflectance optical density of the print, where a lower figure indicates higher light fastness and less fade. The degree of fade is expressed as ΔE where a lower figure indicates higher light fastness. ΔE is defined as the overall change in the CIE colour co-ordinates L, a, b of the print and is expressed by the equation ΔE=(ΔL2+Δa2+Δb2)0.5.
Results
The results of the light fastness tests were as tabulated in Table 2.
From Table 2 it can be seen that Ink 1, containing the compound of Example 2 has better light fastness than the comparative dye on both papers.
Further Compounds
Using synthetic methods analogous to those described for the previous examples the compounds of Examples 4 to 9 were also prepared. The actual experimentally determined lambda max values were as indicated.
Further Inks
The inks described in Tables A and B may be prepared using the Compounds described in the above Examples 1 to 3. Numbers quoted refer to the number of parts of the relevant ingredient and all parts are by weight. The inks may be applied to paper by ink-jet printing.
The following abbreviations are used in Tables A and B:
PG=propylene glycol
DEG=diethylene glycol
NMP=N-methylpyrollidone
DMK=dimethylketone
IPA=isopropanol
MeOH=methanol
2P=2-pyrollidone
MIBK=methylisobutyl ketone
P12=propane-1,2-diol
BDL=butane-2,3-diol
CET=cetyl ammonium bromide
PHO=Na2HPO4
TBT=tertiary butanol
TDG=thiodiglycol
| Number | Date | Country | Kind |
|---|---|---|---|
| 0818568.8 | Oct 2008 | GB | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/GB2009/051333 | 10/8/2009 | WO | 00 | 4/12/2011 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2010/041066 | 4/15/2010 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4124581 | Vor der Bruck et al. | Nov 1978 | A |
| 4908435 | Gregory | Mar 1990 | A |
| 7083670 | Takasaki et al. | Aug 2006 | B2 |
| 7186292 | Yabuki et al. | Mar 2007 | B2 |
| 7192475 | Takasaki et al. | Mar 2007 | B2 |
| 7250079 | Chino et al. | Jul 2007 | B2 |
| 7402201 | Wachi et al. | Jul 2008 | B2 |
| 7431760 | Chino et al. | Oct 2008 | B2 |
| 7465346 | Fukumoto et al. | Dec 2008 | B2 |
| 7491266 | Taguchi et al. | Feb 2009 | B2 |
| 7533978 | Chino et al. | May 2009 | B2 |
| 20110195236 | Foster et al. | Aug 2011 | A1 |
| 20110200800 | Foster et al. | Aug 2011 | A1 |
| Number | Date | Country |
|---|---|---|
| 1 553 147 | Jul 2005 | EP |
| WO 03087238 | Oct 2003 | WO |
| WO 2004113463 | Dec 2004 | WO |
| WO 2010041065 | Apr 2010 | WO |
| Entry |
|---|
| International Search Report and Written Opinion issued Jun. 4, 2010, in PCT Application No. PCT/GB2009/051333. |
| Number | Date | Country | |
|---|---|---|---|
| 20110195236 A1 | Aug 2011 | US |
