GB2421027A - Magenta anthanthrone dyes with at least one water solubilising substituent, and inks for use in ink-jet printing - Google Patents

Magenta anthanthrone dyes with at least one water solubilising substituent, and inks for use in ink-jet printing Download PDF

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Publication number
GB2421027A
GB2421027A GB0523856A GB0523856A GB2421027A GB 2421027 A GB2421027 A GB 2421027A GB 0523856 A GB0523856 A GB 0523856A GB 0523856 A GB0523856 A GB 0523856A GB 2421027 A GB2421027 A GB 2421027A
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formula
ink
optionally substituted
compound
water
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GB2421027B (en
GB0523856D0 (en
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Clive Edwin Foster
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Fujifilm Imaging Colorants Ltd
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Fujifilm Imaging Colorants Ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/66—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfo, esterified sulfo or halosulfonyl groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
    • C09B3/60—Anthanthrones
    • C09B3/64—Preparation from starting materials already containing the anthanthrone nucleus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes

Abstract

A composition comprises: <SL> <LI>(a) a compound of Formula (1) <EMI ID=1.1 HE=49 WI=50 LX=833 LY=657 TI=CF> [wherein: ```R<1>, R<2>, R<3> and R<4> independently are substituents; ```m and p independently are 0 to 3; and ```n and q independently are 0 to 2] or a tautomer thereof, provided that the compound of Formula (1) comprises at least one water solubilising group; and <LI>(b) a liquid media. </SL> Compounds of formula (1) are magenta dyes and their inks may be used to print images on a substrate (eg photographic quality paper) using an ink-jet printer. An ink-jet printer cartridge comprising such inks is also disclosed.

Description

Ma9enta Dyes And Inks For Use In Ink-Jet Printing This invention relates
to compositions and inks for ink jet printers, to dyes, to printing processes, to printed substrates 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. The colour of the inks in any given ink-set is precisely matched so that when printed in combination they are able to reproduce a full colour spectrum With the advent of high-resolution digital cameras and ink-jet printers it is becoming increasingly common for consumers to print off photographs using an ink-jet printer. This avoids the expense and inconvenience of conventional silver halide photography and provides a print quickly and conveniently.
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 do not run or smudge excessively when printed on paper. The inks need to dry quickly to avoid sheets sticking together after they have been printed, but they should not form a crust over the tiny nozzle used in the printer. Storage stability is also important to avoid particle formation that could block the tiny nozzles used in the printer especially since consumers can keep an ink-jet ink cartridge for several months. Furthermore, the resultant images desirably do not fade rapidly on exposure to light or common oxidising gases such as ozone The present invention provides a composition comprising: (a) a compound of Formula (1) (R1)_..
Formula (1) wherein: R1, R2, R3 and R4 independently are substituents, m and p independently are 0 to 3; and n and q independently are 0 to 2 provided that the compound of Formula (1) comprises at least one water solubilising group; and (b) a liquid media.
R1, R2, R3 and R4 are preferably independently selected from: optionally substituted alkyl (preferably C1 -alkyl), optionally substituted alkenyl (preferably C1-alkenyl), optionally substituted alkynyl (preferably C14-alkynyl), optionally substituted alkoxy (preferably C- alkoxy), optionally substituted aryl (preferably phenyl), optionally substituted aryloxy (preferably phenoxy), optionally substituted heterocyclyl (including heteroaryl), polyalkylene oxide (preferably polyethylene oxide or polypropylene oxide), CO2H, SO3H, P03H2, nitro, cyano, halo, ureido, SO2F, hydroxy, ester, sulphate, NRaRb, CORa, CONRaR, NHCORa, carboxyester, sulfone, and SO2NRaRb wherein R8 and Rb are each independently H or optionally substituted alkyl (especially C1-alkyl), SRc, ORc, -NH- R', wherein Rc is optionally substituted alkyl (preferably C14-alkyl), optionally substituted alkenyl (preferably C1-alkenyl), optionally substituted alkynyl (preferably C1-alkynyl), optionally substituted alkoxy (preferably C14-alkoxy), optionally substituted aryl (preferably phenyl), optionally substituted aryloxy (preferably phenoxy), optionally substituted heterocyclyl, polyalkylene oxide (preferably polyethylene oxide or polypropylene oxide), Optional substituents for any of the above substituents may be selected from the same list of substituents.
It is preferred that at least one of the groups represented by R1, R2, R3 and R4 and more preferably at least two of the groups represented by R1, R2, R3 and R4 is SRc, ORc or NHRc wherein Rc is optionally substituted alkyl (preferably C14-alkyl) or optionally substituted aryl (preferably phenyl) and especially optionally substituted phenyl and the optional substituents are selected from the list above.
Preferably m, n, p and q are each independently 0 or 1.
Preferably the sum of m + n + p + q is 2.
It is particularly preferred that at least one, and more preferably two of the groups represented by R1, R2, R3 and R4 is/are SRc where Rc is optionally substituted phenyl, where the optional substituents are selected from the list above.
The compulsory water solubilising group may be bound either directly to the anthanthrone ring system or it may be present as a substituent on one or more of the groups represented by R1, R2, R3 and R4 The water solubilising group present on the compound of Formula (1) may be any group able to increase the aqueous solubility of the compounds of Formula (1). Thus, for example, it may be an ionisable anionic or cationic group or a non-ionic group such as a polyalkylene oxide.
Preferably the compulsory water solubilising group is an anionic ionisable group, more preferably the compulsory water solubilising group is CO2H, SO3H or P03H2.
Preferably the compound of Formula (1) has a solubility in water at 25 C of at least 1%, more preferably the compound of Formula (1) has a solubility in water at 25 C of at least 2.5%, it is particularly preferred that the compound of Formula (1) has a solubility in water at 25oC of at least 5%.
Preferably the compound of Formula (1) is a compound of Formula (2) and salts thereof: Formula (2) wherein: R5 is selected from the group consisting of SRd, ..QRd or NHRd wherein Rd is optionally substituted alkyl (preferably C1-alkyl), optionally substituted phenyl, optionally substituted naphthyl or optionally substituted heterocycyl; x is 1 to 4; and y isO to 9; provided that the compound of Formula (2) comprises at least one water solubilising group.
R5 is preferably SRd.
Rd is preferably optionally substituted phenyl.
R6may be selected from the list given for R1, R2, R3 and R4 above.
Preferably x is 1 or 2, more preferably x is 2.
When x is greater than 1 then preferably there is no more than one R5 per component ring.
When x is 2 or 4 then preferably the compound of Formula (2)is a symmetric under a rotation molecule.
Preferably y is 0 to 4, more preferably y is 0.
Thus a particularly preferred molecule of Formula (2) is of Formula (3) and salts thereof: Formula (3) wherein each R7 is an optionally substituted phenyl and provided that that the compound of Formula (3) comprises at least one water solubilising group.
Each R7 may vary independently of the other, however it is preferred that each R7 is the same The water solubilising group is as described and as preferred above.
Acid and basic groups on the compounds of Formula (1), particularly acid groups, are preferably in the form of a salt Thus, the Formulae shown herein include the compounds in free acid and 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 sodium salts. The compounds of Formula (1) may be converted into a salt using known techniques.
The compounds of Formula (1) may exist in tautomeric forms other than those shown in this specification. These tautomers are included within the scope of the present invention. However, tautomers may not bear a substituent on the hydroxy/enol oxygen.
Preferred compounds of Formula (1) may be prepared, for Example, by the reaction of a thiophenol derivative and a commercially available compound such as 0.1. Vat Orange 3 in the presence of a base. BryJ
Vat Orange 3 The base must be strong enough to form the anionic aromatic nucleophile Solvents such as N-methylpyrrolidone are used and vigorous heating is seldom required. Isolation by precipitation is followed by a sulfonation step where the dried dye molecule is typically added to 20% fuming sulfuric acid, and the mixture heated to 50 C for around 2 hours.
Dilution with water is usually enough to effect precipitation of the desired product.
Preferred liquid media include water, a mixture of water and organic solvent and organic solvent free from water Preferably the liquid media comprises a mixture of water and organic solvent or organic solvent free from water. More preferably the liquid media comprises a mixture of water and organic solvent.
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 5ft50 and 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 C 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 pentane-1,5-diol, 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-alkyl ethers of diols, preferably mono-C1- 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-(2ethoxyethoxy)- 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 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-alkyl and C1-alkyl ethers of diols, more preferably mono- C1-alkyl ethers of diols having 2 to 12 carbon atoms, especially 2-methoxy-2-ethoxy-2-ethoxyethanol.
Examples of further suitable liquid media comprising a mixture of water and one or more organic solvents are described in US 4,963,189, US 4,703, 113, US 4,626,284 and EP 4,251,50A.
When the liquid medium comprises organic solvent free from water, (i.e. less than 1% water by weight) in one embodiment 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 CH2CI2; and ethers, preferably diethyl ether; and mixtures thereof.
When the liquid medium comprises a water-immiscible organic solvent then preferably a polar solvent is preferably included since this enhances solubility of the compound of Formula (1) in the liquid medium. Examples of polar solvents include C1- alcohols.
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-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 medium is organic solvent free from water it is a mixture of 2 to 5 different organic solvents This allows a 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 conventionally used 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.
Although not usually necessary, further colorants may be added to the composition to modify the shade and performance properties It is preferred that the composition according to the invention is ink suitable for use in an ink-jet printer. Ink suitable for use in an ink-jet printer is ink which is able to repeatedly fire through an ink-jet printing head without causing blockage of the fine nozzles.
Ink suitable for use in an ink-jet printer preferably has a viscosity of less than 20 cP, more preferably less than 10 cP, especially less than 5 cP, at 25 C.
Ink suitable for use in an ink-jet printer preferably contains less than 500ppm, more preferably less than 2SOppm, especially less than lOOppm, more especially less than loppm in total of divalent and trivalent metal ions (other than any divalent and trivalent metal ions bound to a colorant of Formula (1) or any other component of the ink).
Preferably ink suitable for use in an ink-jet printer has been filtered through a filter having a mean pore size below 10jtm, more preferably below 3tm, especially below 2Lm, more especially below 1 jtm. 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 500ppm, more preferably less than 25Oppm, especially less than lOOppm, more especially less than 1 Oppm in total of halide ions Preferred compositions comprise: (a) from 0.01 to 30 parts of compounds of Formula (1); and (b) from 70 to 99.99 parts of a liquid medium; wherein all parts are by weight.
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, 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 10% 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.
The inks may be incorporated in an ink-jet printer as a high concentration magenta ink, a low concentration magenta ink or both a high concentration and a low concentration ink. In the latter case this can lead to improvements in the resolution and quality of printed images. Thus the present invention also provides a composition 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).
Compositions and inks according to the present invention yield prints that display a good fastness to water, ozone and light. In particular, prints prepared using these inks display excellent ozone fastness.
A second aspect of the invention provides a compound of Formula (2) and salts thereof Formula (2) wherein: R5 is selected from the group consisting of SRd, ..O..Rd or NHRd wherein Rd is optionally substituted alkyl (preferably C1-aIkyI), optionally substituted phenyl, optionally substituted naphthyl or optionally substituted heterocycyl; xislto4;and y isO to9, provided that the compound of Formula (2) comprises at least one water solubilising group.
R5 is preferably SRd.
Rd is preferably optionally substituted phenyl.
R6 may be selected from the list given for R1, R2, R3 and R4 in the first aspect of the invention.
Preferably x is 1 or 2, more preferably x is 2.
When x is greater than 1 then preferably there is no more than one R5 per component ring When x is 2 or 4 then preferably the compound of Formula (2) is a symmetrical molecule.
Preferably y is 0 to 4, more preferably y is 0.
Thus a particularly preferred molecule of Formula (2) is of Formula (3) and salts thereof R7S II )LA SR7 Formula (3) wherein each R7 is an optionally substituted phenyl and provided that that the compound of Formula (3) comprises at least one water solubilising group.
Each R7 may vary independently of the other, however it is preferred that each R7 is the same.
Preferably the water solubilising group is as preferred in the first aspect of the invention.
Acid and basic groups on the compounds of Formula (2), particularly acid groups, are preferably in the form of a salt. Thus, the Formulae shown herein include the compounds in free acid and 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 sodium salts. The compounds of Formula (2) may be converted into a salt using known techniques.
The compounds of Formula (2) may exist in tautomeric forms other than those shown in this specification. These tautomers are included within the scope of the present invention.
A third aspect of the invention provides a process for forming an image on a substrate comprising applying ink suitable for use in an ink-jet printer, according to the first aspect of the invention, thereto by means of an ink-jet printer.
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 W000/48938 and International Patent Application W000/55089 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. Glossy papers are especially preferred.
Photographic quality paper is particularly preferred.
A fourth aspect of the present invention provides a material 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 printed with a composition according to the first aspect of the invention or by means of a process according to the third aspect of the invention.
It is especiaHy preferred that the printed material of the fourth aspect of the invention is a print on photographic quality paper.
A fifth aspect of the present invention provides an ink-jet printer cartridge comprising a chamber and an ink wherein the ink is in the chamber and the ink is as defined in the first aspect of the present invention. The cartridge may contain a high concentration ink and a low concentration ink, as described in the first aspect of the invention, in different chambers.
The invention is further illustrated by the following Examples in which all parts and percentages are by weight unless otherwise stated.
Example 1
Preparation of: CH3 OH Hg 0 CH3 Stage 1 Preparation of: CH3 CH3 A mixture of 4-methylbenzenethiol (42.5g) and potassium hydroxide (28.8g) in dimethylformamide (400m1) was stirred at 60 C for 1 hour. Dibromoanthanthrone (40.25g) was added portion-wise and the reaction was continued for a further 1.5 hours at 60 C.
After drowning into methanol (800m1), filtering and washing with methanol, the product was dried at 70 C to give 44.4g of a purple solid Preparation of the title compound: The product of stage 1(5.5g) was added cautiously to 98% sulphuric acid (4Oml) and the resultant mixture warmed to 50 C and stirred at this temperature for 3 hours. After cooling to room temperature the reaction mixture was added to ice and water (500g), and the precipitated product filtered. The potassium salt of the product was prepared by dissolving in water, filtering from insoluble residue, and basifying with potassium carbonate.
The crude precipitated product was separated and purified by dissolving in water and salting with potassium chloride. Removal of salts from the product was effected by dialysis, and the dialysed solution was evaporated to give 4.7g of lustrous violet solid with a Xmax(H20) 542nm.
Comparative Examples
The Comparative Examples chosen represent generic examples of the type of magenta dyes currently used in ink-jet printing.
Comparative Dye Examplel was prepared as described in Example 1 of US5599386
COH NN
HN)N)N9 CO2H Comparative Dye Example 1 Comparative Dye Example 2 was prepared as described for Dye 101 in US5824785.
HO H_1SO3H N-_4 N SO3H H2N
HO HO-ç SO3H
Comparative Dye Example 2
Example 2
Preparation of Inks Inks were prepared from the Comparative Dyes and the dye of Example 1 by dissolving 3 g of dye in 97 ml of a l(quid medium consisting of 5 parts 2-pyrrolidone; 5 parts thiodiethylerie glycol; 1 part SurfynolTM 465 and 89 parts water and adjusting the pH to between pH 8 to 9 with sodium hydroxide. SurfynolTM 465 is a surfactant from Air Products.
Inks such as this would have a viscosity of less than 20 cP 25 C; a surface tension in the range 20-65 dynes/cm at 25 C; less than 500ppm in total of divalent and trivalent metal ions (other than any divalent and trivalent metal ions bound to the colorant of or any other component of the ink); and less than 500ppm in total of halide ions.
Ink-jet Printing Inks prepared as described above were filtered through a 0.45 micron nylon filter and then incorporated into empty print cartridges ira syringe.
Theenks were then printed on to EpsonPremium Glossy Photo Paper (SEC PM) and CanonPremium PR1O1 Photo Paper (PR1O1).
The prints so formed were tested for ozone fastness by exposure to 1 ppm ozone at 40 C, 50% relative humidity for 24hrs in a Hampden 903 Ozone cabinet. Fastness of the printed ink to ozone is judged by the difference in the optical density before and after exposure to ozone.
Optical density measurements were performed using a Gretag spectrolino spectrophotometer set to the following parameters: Measuring Geometry: 450/00 Spectral Range: 380 - 730nm Spectral Interval: lOnm Illuminant D65 Observer: 2 (CIE 1931) Density: Ansi A External Filler. None Ozone fastness was assessed by the percentage change in the optical density of the print, where a lower figure indicates higher fastness. Results are shown in Table 1
Table 1
Example OF (SEC PM) OF (PR 101) Inki 2 6 Comparative Ink 1 27 19 Comparative Ink 2 81 69 Table 1 shows that a print formed with a dye/ink of the present invention has a superior ozone fastness.
Further Inks The inks described in Tables A and B may be prepared. Numbers quoted in the second column onwards 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-methyl pyrrolidone DMK = dimethylketone IPA = sopropanol MEOH = methanol 2P = 2-pyrrolidone MIBK = methylisobutyl ketone P12 = propane-i,2-diol BDL = butane-2,3-diol CET= cetyl ammonium bromide PHO = Na2HPO4 and TBT = tertiary butanol TDG = thiodiglyco!
TABLE A
Dye Water PG DEC NMP DMK NaOH Na IPA MEOH 2P MIBK Content _______ _____ _____ _____ ______ Stearate ____ ________ ________ 2.0 80 5 6 4 5 3.0 90 5 5 0.2 10.0 85 3 3 3 5 1 21 91 8 1 3.1 86 5 0.2 4 5 11 81 9 0.5 0.5 9 2.5 60 4 15 3 3 6 10 5 4 65 20 10 2.4 75 5 4 5 6 5 4.1 80 3 5 2 10 0.3 3.2 65 5 4 6 5 4 6 5 51 96 4 10.8 90 5 5 10.0 80 2 6 2 5 1 4 1.8 80 5 15 2.6 84 11 5 3.3 80 2 10 2 6 12.0 90 7 0.3 3 5.4 69 2 20 2 1 3 3 6.0 91 ___ 4 ___ ___ ______ ___ _____ 5 _____
TABLE B
Dye Water PG DEG NMP CET TBT TDG BDL PHO 2P P12 Content ________ 3.0 80 15 0.2 5 90 5 1.2 5 1.5 85 5 5 015 5.0 02 2.5 90 6 4 0.12 31 82 4 8 0.3 6 0.9 85 10 5 0.2 90 5 5 0.3 4.0 70 10 4 1 4 11 2.2 75 4 10 3 2 6 91 6 3 9.0 76 9 7 3.0 0.95 5 5.0 78 5 11 6 5.4 86 7 7 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5 2.0 90 10 2 88 10 78 5 12 5 8 70 2 8 15 5 80 8 12 80 10 ___ ___ ___ ___ ___ ___ ___

Claims (17)

  1. Claims 1 A composition comprising: (a) a compound of Formula (1) (R1)
    Formula (1) wherein: R1, R2, R3 and R4 independently are substituents; m and p independently are 0 to 3; and n and q independently are 0 to 2: provided that the compound of Formula (1) comprises at least one water solubilising group; and (b) a liquid media.
  2. 2. A composition according to claim 1 wherein at least one of the groups represented by R1, R2, R3 and R4 is SRG, ORc or NHRc wherein Rc is optionally substituted C14-alkyl
  3. 3. A composition according to either claim 1 or claim 2 wherein the sum of m + n + p + q is 2.
  4. 4 A composition according to any one of the preceding claims wherein two of the groups represented by R1, R2, R3 and R4are SRc where Rc is optionally substituted phenyL
  5. 5. A composition according to any one of the preceding claims wherein the compound of Formula (1) has a solubility in water at 25 C of at least 1%.
  6. 6. A composition according to claim 1 wherein the compound of Formula (1) is a compound of Formula (2) and salts thereof: Formula (2) wherein* R5 is selected from the group consisting of SRd, ORd or NHRd wherein Rd is optionally substituted C1-alkyl, optionally substituted phenyl, optionally substituted naphthyl or optionally substituted heterocycyl; xis 1 to4,and yis0to9; provided that the compound of Formula (2) comprises at least one water solubilising group.
  7. 7. A composition according to claim 6 wherein the compound of Formula (2) is of Formula (3) and salts thereof: Formula (3) wherein each R7 is an optionally substituted phenyl and provided that that the compound of Formula (3) comprises at least one water solubilising group.
  8. 8. A composition according to claim 7 wherein each R7 is the same.
  9. 9. A composition according to any one of the preceding claims wherein the liquid media comprises a mixture of water and organic solvent.
  10. 10. A composition according to any one of the preceding claims which is ink suitable for use in an ink-jet printer
  11. 11. A compound of Formula (2) and salts thereof.
    Formula (2) wherein R5 is selected from the group consisting of SRd, ORd or NHRd wherein Rd is optionally substituted C1-alkyl, optionally substituted phenyl, optionally substituted naphthyl or optionally substituted heterocycyl; x is 1 to 4; and yisoto9; provided that the compound of Formula (2) comprises at least one water solubilising group.
  12. 12. A compound according to claim 11 of Formula (3) and salts thereof:
    R
    Formula (3) wherein each R7 is an optionally substituted phenyl and provided that that the compound of Formula (3) comprises at least one water solubilising group.
  13. 13. A compound according to either claim 11 or claim 12 wherein each R7 is the same.
  14. 14. A process for forming an image on a substrate comprising applying ink suitable for use in an ink-jet printer, according to claim 10, thereto by means of an ink-jet printer.
  15. 15. A material printed by means of a process according to claim 14.
  16. 16. A material according to claim 15 which is a print on photographic quality paper
  17. 17. An ink-jet printer cartridge comprising a chamber and an ink wherein the ink is in the chamber and the ink is as defined in claim 10.
GB0523856A 2004-12-02 2005-11-21 Magenta dyes and inks for use in ink-jet printing Expired - Fee Related GB2421027B (en)

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US7479181B2 (en) * 2006-07-31 2009-01-20 Hewlett-Packard Development Company, L.P. Inkjet ink composition and method of making the same
US7476271B2 (en) * 2006-07-31 2009-01-13 Hewlett-Packard Development Company, L.P. Inkjet ink set

Citations (1)

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Publication number Priority date Publication date Assignee Title
JPH09122470A (en) * 1995-10-28 1997-05-13 Sanyo Shikiso Kk Pigment dispersant

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US1805913A (en) * 1926-10-13 1931-05-19 Gen Aniline Works Inc New alkoxy derivatives of anthanthrone and process of making same
US1876972A (en) * 1928-02-24 1932-09-13 Gen Aniline Works Inc Production of monoaminoanthanthrones and derivatives thereof
US1897427A (en) * 1928-03-10 1933-02-14 Gen Aniline Works Inc Vat dyestuffs of the anthanthrone series and process of preparing the same
US1876973A (en) * 1928-07-28 1932-09-13 Gen Aniline Works Inc Substitution products of anthanthrones
US2191685A (en) * 1935-06-27 1940-02-27 Gen Aniline & Film Corp Process for producing nitrogenous condensation products of the anthrone series
US2292551A (en) * 1940-01-26 1942-08-11 Du Pont Naphthostyril-5-carboxylic acid
US2645645A (en) * 1950-12-20 1953-07-14 Gen Aniline & Film Corp Chloromethylation of arylaminopolycyclic quinones
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US7270700B2 (en) 2007-09-18
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US20060117990A1 (en) 2006-06-08
GB0523856D0 (en) 2006-01-04

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