Indian Patents. 258661:HIGH-LIGHT FASTNESS INKS FOR DIGITAL TEXTILE PRINTING

Title of Invention	HIGH-LIGHT FASTNESS INKS FOR DIGITAL TEXTILE PRINTING
Abstract	Disclosed are aqueous printing inks that are used for inkjet textile printing and contain one of several compounds of general formula (I), wherein A,B, R1 to R6, and D have the meaning indicated in claim 1, methods for the production thereof, and the use thereof for inkjet textile printing.

Full Text	DyStar Textilfarben GmbH & Co. Deutschland KG DYS 2004/D 501 Dr. Ku High-lightfastness inks for digital textile printing Digital printing techniques will become increasingly important in the future both in the textile segment and in the nontextile segment. The altered market requirements in conventional textile printing call for more flexibility in design, color, and delivery time. One response to this development is digital inkjet technology. By making it possible to print directly from the computer via the printing nozzles onto the textiles without the need to prepare printing screens, this new technology is improving printing process flexibility, efficiency, and environmental compatibility. It allows substantially integrated operations, shortens printing times, and meets the demand for rapid reaction to market developments and for fewer intermediate stages in the manufacturing operation. The inkjet process normally uses aqueous inks which are sprayed as small droplets directly onto the substrate. There is a division between a continuous flow process, in which ink droplets are generated without interruption and guided onto the substrate through an electrical field, as a function of the pattern to be printed, and an interrupted inkjet or drop-on- demand process, in which the ink is ejected only where a colored dot is to be placed. The latter process employs either a piezoelectric crystal or a heating element (bubblejet or thermal jet process) to exert pressure on the ink system and so to force out a drop of ink. Such procedures are described in Text. Chem. Color, Volume 19 (8), pages 23 ff and Volume 21 pages 27 ff. Other drop-on-demand processes include the "flatjet process", which is described for example in WO 99/46126, where piezoelectrically controlled vibration of a dye-filled needle forces ink droplets onto the substrate, and the "valvejet process" in which the inkjet and hence the pixel distribution is regulated via a valve, a process of this kind being described for example in US 4555719. This highly sensitive microtechnology requires the development of tailor- made dye preparations (inks) which meet, for example, the exacting requirements in terms of purity, particle size, viscosity, surface tension, conductivity, physicochemical stability, thermophysical properties, pH, absence of foam and microfoam, color strength, fastness level, and storage stability. Commercially customary textile dyes in the form of their powder, granule or liquid formulations, as are used for conventional analog textile printing, contain significant amounts of electrolyte, deduster and standardizer, which lead to massive problems in inkjet printing. Moreover, dye inks, such as are used for nontextile materials, such as paper, wood, plastics, ceramic, etc., for example, give only unsatisfactory results in terms of application properties and also color yield and print fastnesses on textile material. Inkjet inks based on disperse dyes have a number of performance deficiencies which relate to the dispersion stability of the inks and the fastnesses achieved in printing, especially the lightfastness of the resultant prints. It was an object of the present invention, therefore, to provide printing inks which do not have the abovementioned disadvantages. It has now surprisingly been found that inks based on isoindolenine dyes, such as are known from EP 684 289, provide outstanding results. The present invention accordingly provides new aqueous printing inks for textile printing by the inkjet process, which comprise an isoindolenine dye of the formula (I) in which A is N or a cyanomethylene radical, B is a radical of the formula C(CN)COOR5 or N-R6, 1 4 R to R independently of one another are hydrogen, halogen, unsubstituted or substituted C1-C8 alkyl or C5-C6 cycloalkyl, uninterrupted or oxygen-interrupted C1-C10 alkoxy, unsubstituted or substituted C6-C10 aryloxy, CF3, or unsubstituted or substituted dialkylamine, or pairs of adjacent R1 to R4 radicals together with the aromatic ring carbon atoms form a fused benzene or naphthalene ring, which where appropriate may be substituted further, examples of possible substituents including halogen or C1-C4 alkyl, R5 is an unsubstituted or substituted and uninterrupted or oxygen- interrupted, saturated or unsaturated C1-C20 alkyl radical, C6-C10 aryl C1-C10 alkyl or hetarylalkyl, R6 is unsubstituted or substituted and uninterrupted or oxygen- interrupted C1-C20 alkyl, cycloalkyl, cycloalkylalkyl or aralkyl, and the ring D is unsubstituted or carries at least one substituent which where appropriate, together with a further substituent in ortho position and the ring carbon atoms, forms a fused benzene or naphthalene ring. Examples of suitable radicals R1 to R4 include the following: hydrogen, chloro, bromo, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, n- propoxy, n-butoxy, methoxyethyl, methoxyethoxyethyl, ethoxyethyl, ethoxyethoxyethyl, butoxyethyl, phenoxy, 2-methylphenoxy, 3- methylphenoxy, 4-methylphenoxy, dimethylamino, diethylamino and bis-(2- cyanoethyl)amino. Examples of suitable radicals R5 include the following: methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, 2-methoxyethyl, 2-ethoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2-allyloxyethyl, 2-(2-methoxyethoxy)ethyl, 2-(2-ethoxyethoxy)ethyl, 2-(2-methoxyethoxy)ethyl, 2-cyanoethyl, 2-(cyanoethoxy)ethyl, 4-(2-cyano- ethoxy)butyl, 2-ethylhexyl, benzyl, phenylethyl. 3-phenylpropyl, phenoxy- ethyl and furfuryl. Suitable branched radicals R5 include preferably those having a methyl side chain, such as: isobutyl, tert-butyl, isopentyl, 1-methoxy-2-propanol and 1-ethoxy-2-propanol. Examples of suitable radicals R include the following: methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, 2-ethylhexyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3-phenoxypropyl, 3-(2-phenoxyethoxy)- propyl, cyclohexyl, cyclohexylmethyl, benzyl and 2-phenylethyl. Preferred dyes of the formula (I) are those in which R1 and R2 independently of one another are hydrogen, CI, Br, methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, uninterrupted C1-C10 alkoxy or C1-C10 alkoxy interrupted by 1 to 2 oxygens; unsubstituted or substituted phenoxy, CF3 or a di(C1-C4)-alkylamino group, R3 and R4 have the definition of R1 and R2 or together with the ring carbon atoms form a fused benzene ring, R5 is a C1-C12 alkyl which is unsubstituted or substituted by CI, by CN or by unsubstituted or substituted phenoxy and is uninterrupted or interrupted by 1 to 2 oxygen atoms, or is C6-C10 aryl-C1-C10 alkyl or hetarylalkyl, R6 is a saturated or unsaturated C1-C12 alkyl which is unsubstituted or substituted by unsubstituted or substituted phenoxy and is uninterrupted or interrupted by 1 to 2 oxygens, and the ring D is unsubstituted or substituted by CN, halogen atoms, in particular 1 to 4 CI atoms, 1 to 2 C1-C10 alkyl radicals and/or 1 to 2 C1-C10 alkoxy radicals, or an unsubstituted or substituted phenyl radical. In particular, however, the ring D is unsubstituted. Particularly preferred dyes of the formula (I) are those of the formula (II) in which R1 to R5 are as defined above, R1 to R4 independently of one another preferably being hydrogen, chloro, methyl, ethyl, isopropyl, tert- butyl, cyclohexyl, methoxy, ethoxy, n-propoxy, n-butoxy, methoxyethyl, ethoxyethyl, butoxyethyl or phenoxy and R5 preferably being n-butyl, isobutyl, n- or isopentyl, hexyl, octyl, 2-ethyl- hexyl, methoxyethyl, ethoxyethyl, butoxyethyl, butoxyethoxyethyl. Further preference is given to dyes of the formula (I) that conform to the formula (III) methyl, isopropyl, tert-butyl, cyclohexyl, methoxy, ethoxy, n-propoxy, n-butoxy, methoxyethyl, ethoxyethyl, butoxyethyl or phenoxy and R preferably being methyl, ethyl, propyl, isopropyl, allyl, n-butyl, isobutyl, n- or isopentyl, hexyl, octyl, 2-ethylhexyl, cyclohexyl, methoxypropyl, ethoxypropyl, 2-phenoxyethyl, 3-phenoxypropyl, 2-phenoxyethoxypropyl, phenylethyl. Besides the dye the printing inks contain 0.1% to 20% of dispersants. Examples of suitable dispersants include sulfonated and sulfomethylated lignins, formaldehyde condensates of aromatic sulfonic acids, formal- dehyde condensates of unsubstituted or substituted phenol derivatives, polyacrylates and their copolymers, polyethers containing styrene oxide, modified polyurethanes, reaction products of alkylene oxides with alkylatable compounds such as, for example, fatty alcohols, fatty amines, fatty acids, carboxamides, resin acids and also unsubstituted or substituted phenols. For the inks to be used in the continuous flow process a conductivity of 0.5 to 25 mS/cm can be set by adding electrolyte. Examples of suitable electrolytes include the following: lithium nitrate or potassium nitrate. The dye inks of the invention may include organic solvents with a total content of 1-60%, preferably of 5-40% by weight. Examples of suitable organic solvents are alcohols, e.g., methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, tert- butanol, 1-pentanol, benzyl alcohol, 2-butoxyethanol, 2-(2-methoxy- ethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol; polyhydric alcohols, e.g.: 1,2-ethanediol, 1,2,3-propanetriol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,2-octanediol, trimethylolethane, trimethylolpropane; polyalkylene alcohols, e.g.: polyethylene glycol and polypropylene glycol and their copolymers, alkylene glycols having 2 to 8 alkylene groups and also corresponding thioether compounds, e.g.: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyl diglycol, butyl triglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol; The textile substrate is pretreated prior to printing with thickeners, which prevent the motifs running when the printing ink is applied; examples of such thickeners include sodium alginates, modified polyacrylates or highly etherified galactomannans; and/or with substances which increase the fixing yield. These pretreatment reagents are applied uniformly to the textile substrate in a defined amount using suitable applicators, such as with a 2- or 3-roll padder, for example, with contactless spray technologies, by means of foam application, or with appropriately adapted inkjet technologies, and then dried. After the textile fiber material has been printed it can be dried at 80 to 150°C and/or subsequently fixed. The fixing of the inkjet prints prepared with disperse dyes takes place at elevated temperature, using saturated steam, using superheated steam, using hot air, using compressed steam, using microwaves, using infrared radiation, using laser or electron beams, or using other suitable energy transfer techniques. Fixing may be followed by a print aftertreatment, which leads to an improvement in fastness properties and also to an immaculate white ground. Particularly on synthetic fiber materials the prints prepared with the dye inks of the invention possess high color strength, good cold and hot lightfastness, very good wetfastness properties, such as fastness to washing, water, saltwater, weather fastness and perspiration fastness, and also good fastness to heat setting and pleating, and crock fastness. The examples which follow serve to illustrate the invention. Parts and percentages are by weight unless otherwise noted. The relationship between parts by weight and parts by volume is that of the kilogram to the liter. General procedure: Preparation of an ink paste (containing 25% of dye): 125 g of dye are combined together with X weight equivalents (1 weight equivalent corresponds to 125 g) of dispersant/dispersant mixture and 375-125X g of demineralized water and the mixture is milled in an agitated ball mill so that the mean particle size is than 1 urn. It is possible for further additives such as biocides, defoamers, etc. and also parts of the organic solvents used to be added even at the ink paste milling stage. The other constituents of the ink (organic solvents, other additives, water) are added to the ink paste thus prepared (containing 25% of dye) and the components are combined thoroughly by beating in a dissolver. Once they have been filtered through a standard commercial filter paper (Macherey- Nagel MN-614) the inks are ready for use. Example 1 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 3.5% of the dye (1) 2.5% of dispersant Disperbyk 190 30% of 1,5-pentanediol 5% of diethylene glycol monomethyl ether 0.01% of biocide Mergal K9N 58.99% of water using a drop-on-demand (piezo) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. Example 2 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 2% of the dye (2) 1 % of dispersant Tego Dispers 740 W 20% of glycerol 0.01% of biocide Mergal K9N 76.99% of water using a drop-on-demand (bubblejet) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 3 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 7% of the dye (2) 3% of dispersant Tamol 30% of diethylene glycol 0.01% of biocide Mergal K9N 59.99% of water using a drop-on-demand (piezo) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 4 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 1% of the dye (2) 0.6% of dispersant Tego Dispers 760 W 15% of polyethylene glycol 400 0.01% of biocide Mergal K9N 83.39% of water using a drop-on-demand (bubblejet) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 5 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 5% of the dye (2) 2% of dispersant Ultrazine NA (ligninsulfonate, borregaard) 15% of polyethylene glycol 400 0.01% of biocide Mergal K9N 77.99% of water using a drop-on-demand (piezo) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 6 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 4% of the dye (2) 1% of dispersant Ultrazine NA (ligninsulfonate, borregaard) 1% of dispersant Tego Dispers 650 0.01% of biocide Mergal K9N 83.99% of water using a drop-on-demand (flatjet) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 7 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 3% of the dye (3) 3% of dispersant Disperbyk 190 10% of polyethylene glycol 400 20% of polypropylene glycol 0.01% of biocide Mergal K9N 63.99% of water using a drop-on-demand (piezo) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 8 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 9% of the dye (3) 3% of dispersant Tego Dispers 740 W 5% of polyethylene glycol 200 10% of ethylene glycol 0.01% of biocide Mergal K9N 72.99% of water using a drop-on-demand (piezo) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 9 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 5% of the dye (4) 5% of dispersant Tamol 10% of 1,2-hexanediol 20% of N-methylpyrrolidone 0.01% of biocide Mergal K9N 59.99% of water using a drop-on-demand (bubblejet) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 10 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 2% of the dye (3) 2% of the dye (4) 2% of dispersant Ultrazine NA (ligninsulfonate, borregaard) 10% of diethylene glycol 20% of sulfolane 2% of urea 0.01% of biocide Mergal K9N 61.99% of water using a drop-on-demand (bubblejet) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 11 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 1.5%of the dye(3) 2.5% of the dye (4) 2% of dispersant Tego Dispers 760 W 0.5% of dispersant Tego Dispers 650 20% of glycerol 5% of diethylene glycol 0.2% of Surfynol 104 E (Air Products) 0.01% of biocide Mergal K9N 68.29% of water using a drop-on-demand (piezo) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow-orange print of high brightness having an outstanding durability and hot lightfastness properties. Example 12 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 3% of the dye (5) 2% of dispersant Ultrazine NA (ligninsulfonate, borregaard) 15% of propylene glycol 5% of polyethylene glycol 800 0.01% of biocide Mergal K9N 74.99% of water using a drop-on-demand (valvejet) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives a yellow, fluorescent print of high brightness having an outstanding durability and hot lightfastness properties. Example 13 A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12% strength bean gum ether solution and 5 g/l of monosodium phosphate in water and then dried. The liquor pickup is 70%. The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing 6% of the dye (6) 1.5% of dispersant Disperbyk 190 10% of 2-propanol 20% of polyethylene glycol 200 0.01% of biocide Mergal K9N 62.49% of water using a drop-on-demand (piezo) inkjet printing head. The print is fully dried. Fixing takes place by means of superheated steam at 175°C for 7 minutes. The print is then subjected to an alkalinically reductive aftertreatment, rinsed warm and then dried. This gives an orange print of high brightness having an outstanding durability and hot lightfastness properties. WE CLAIM 1. An aqueous printing ink for textile printing by the inkjet process, comprising one or more dyes of the formula (I) in which A is N or a cyanomethylene radical, B is a radical of the formula C(CN)COOR5 or N-R6, R1 to R4 independently of one another are hydrogen, halogen, unsubstituted or substituted C1-C8 alkyl or C5-C6 cycloalkyl, uninterrupted or oxygen- interrupted C1-C10 alkoxy, unsubstituted or substituted C6-C10 aryloxy, CF3, or unsubstituted or substituted dialkylamine, or pairs of adjacent R1 to R4 radicals together with the aromatic ring carbon atoms form a fused benzene or naphthalene ring, which where appropriate is substituted further, R5 is an unsubstituted or substituted and uninterrupted or oxygen-interrupted, saturated or unsaturated C1-C20 alkyl radical, C6-C10 aryl C1-C10 alkyl or hetarylalkyl, R6 is unsubstituted or substituted and uninterrupted or oxygen-interrupted C1-C20 alkyl, cycloalkyl, cycloalkylalkyl or aralkyl, and the ring D is unsubstituted or carries at least one substituent which where appropriate, together with a further substituent in ortho position and the ring carbon atoms, forms a fused benzene or naphthalene ring. 2. An aqueous printing ink for textile printing by the inkjet process, comprising dyes of the formula (I) as claimed in claim 1, wherein R1 and R2 independently of one another are hydrogen, CI, Br, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, uninterrupted C1-C10 alkoxy or C1-C10 alkoxy interrupted by 1 to 2 oxygens; unsubstituted or substituted phenoxy, CF3 or a di(C1-C4)-alkylamino group, R3 and R4 have the definition of R1 and R2 or together with the ring carbon atoms form a fused benzene ring, R5 is a C1-C12 alkyl which is unsubstituted or substituted by CI, by CN or by unsubstituted or substituted phenoxy and is uninterrupted or interrupted by 1 to 2 oxygen atoms, or is C6-C10 aryl-C1-C10 alkyl or hetarylalkyl, R6 is a saturated or unsaturated C1-C12 alkyl which is unsubstituted or substituted by unsubstituted or substituted phenoxy and is uninterrupted or interrupted by 1 to 2 oxygens, and ring D is unsubstituted or substituted by CN, halogen atoms, in particular 1 to 4 CI atoms, 1 to 2 C1-C10 alkyl radicals and/or 1 to 2 C1-C10 alkoxy radicals, or a phenyl radical, which are each uninterrupted or interrupted by 1 to 2 oxygen atoms. 3. An aqueous printing ink for textile printing by the inkjet process, comprising dyes as claimed in claim 1 of the formula (II) wherein R1 to R5 are as defined in claim 1. 4. An aqueous printing ink for textile printing by the inkjet process, comprising dyes as claimed in claim 1 of the formula (III) wherein R1 to R5 are as defined in claim 1. 5. An aqueous printing ink for textile printing by the inkjet process, comprising dyes as claimed in claim 1 of the formula (IV) wherein R1 to R4 and R6 are as defined in claim 1. 6. An aqueous printing ink for textile printing by the inkjet process, comprising dyes as claimed in claim 1 of the formula (V) wherein R1 to R4 and R6 are as defined in claim 1. 7. An aqueous printing ink for textile printing by the inkjet process as claimed in at least one of claims 1 to 6, comprising one or more disperse dyes of the formula (I) in amounts of 0.01% by weight to 40% by weight, based on the total weight of the ink, 8. An aqueous printing ink for textile printing by the inkjet process as claimed in at least one of claims 1-7, containing 0.1%-20% by weight of a dispersant and also 1% to 60% of organic solvents, based on the total weight of the ink. 9. A method of printing textile fiber materials by the inkjet process, which comprises employing a printing ink as claimed in at least one of claims 1 to 8. ABSTRACT TITLE : HIGHLIGHT FASTNESS INKS FOR DIGITAL TEXTILE PRINTING Disclosed are aqueous printing inks that are used for inkjet textile printing and contain one of several compounds of general formula (I), wherein A,B, R1 to R6, and D have the meaning indicated in claim 1, methods for the production thereof, and the use thereof for inkjet textile printing.

Full Text

DyStar Textilfarben GmbH & Co. Deutschland KG DYS 2004/D 501 Dr. Ku
High-lightfastness inks for digital textile printing
Digital printing techniques will become increasingly important in the future
both in the textile segment and in the nontextile segment.
The altered market requirements in conventional textile printing call for
more flexibility in design, color, and delivery time. One response to this
development is digital inkjet technology. By making it possible to print
directly from the computer via the printing nozzles onto the textiles without
the need to prepare printing screens, this new technology is improving
printing process flexibility, efficiency, and environmental compatibility. It
allows substantially integrated operations, shortens printing times, and
meets the demand for rapid reaction to market developments and for fewer
intermediate stages in the manufacturing operation.
The inkjet process normally uses aqueous inks which are sprayed as small
droplets directly onto the substrate. There is a division between a
continuous flow process, in which ink droplets are generated without
interruption and guided onto the substrate through an electrical field, as a
function of the pattern to be printed, and an interrupted inkjet or drop-on-
demand process, in which the ink is ejected only where a colored dot is to
be placed. The latter process employs either a piezoelectric crystal or a
heating element (bubblejet or thermal jet process) to exert pressure on the
ink system and so to force out a drop of ink. Such procedures are
described in Text. Chem. Color, Volume 19 (8), pages 23 ff and Volume 21
pages 27 ff. Other drop-on-demand processes include the "flatjet process",
which is described for example in WO 99/46126, where piezoelectrically
controlled vibration of a dye-filled needle forces ink droplets onto the
substrate, and the "valvejet process" in which the inkjet and hence the pixel
distribution is regulated via a valve, a process of this kind being described
for example in US 4555719.
This highly sensitive microtechnology requires the development of tailor-
made dye preparations (inks) which meet, for example, the exacting
requirements in terms of purity, particle size, viscosity, surface tension,
conductivity, physicochemical stability, thermophysical properties, pH,
absence of foam and microfoam, color strength, fastness level, and storage
stability. Commercially customary textile dyes in the form of their powder,

granule or liquid formulations, as are used for conventional analog textile
printing, contain significant amounts of electrolyte, deduster and
standardizer, which lead to massive problems in inkjet printing. Moreover,
dye inks, such as are used for nontextile materials, such as paper, wood,
plastics, ceramic, etc., for example, give only unsatisfactory results in terms
of application properties and also color yield and print fastnesses on textile
material.
Inkjet inks based on disperse dyes have a number of performance
deficiencies which relate to the dispersion stability of the inks and the
fastnesses achieved in printing, especially the lightfastness of the resultant
prints.
It was an object of the present invention, therefore, to provide printing inks
which do not have the abovementioned disadvantages.
It has now surprisingly been found that inks based on isoindolenine dyes,
such as are known from EP 684 289, provide outstanding results.
The present invention accordingly provides new aqueous printing inks for
textile printing by the inkjet process, which comprise an isoindolenine dye
of the formula (I)
in which
A is N or a cyanomethylene radical,
B is a radical of the formula C(CN)COOR5 or N-R6,
1 4
R to R independently of one another are hydrogen, halogen,
unsubstituted or substituted C1-C8 alkyl or C5-C6 cycloalkyl,
uninterrupted or oxygen-interrupted C1-C10 alkoxy, unsubstituted or
substituted C6-C10 aryloxy, CF3, or unsubstituted or substituted

dialkylamine, or pairs of adjacent R1 to R4 radicals together with the
aromatic ring carbon atoms form a fused benzene or naphthalene

ring, which where appropriate may be substituted further, examples
of possible substituents including halogen or C1-C4 alkyl, R5 is an unsubstituted or substituted and uninterrupted or oxygen-
interrupted, saturated or unsaturated C1-C20 alkyl radical, C6-C10
aryl C1-C10 alkyl or hetarylalkyl,
R6 is unsubstituted or substituted and uninterrupted or oxygen-
interrupted C1-C20 alkyl, cycloalkyl, cycloalkylalkyl or aralkyl, and
the ring D is unsubstituted or carries at least one substituent which where
appropriate, together with a further substituent in ortho position and the ring
carbon atoms, forms a fused benzene or naphthalene ring.

Examples of suitable radicals R1 to R4 include the following: hydrogen,
chloro, bromo, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, n-
propoxy, n-butoxy, methoxyethyl, methoxyethoxyethyl, ethoxyethyl,
ethoxyethoxyethyl, butoxyethyl, phenoxy, 2-methylphenoxy, 3-
methylphenoxy, 4-methylphenoxy, dimethylamino, diethylamino and bis-(2-
cyanoethyl)amino.

Examples of suitable radicals R5 include the following: methyl, ethyl,
n-propyl, isopropyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
n-decyl, 2-methoxyethyl, 2-ethoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl,
2-allyloxyethyl, 2-(2-methoxyethoxy)ethyl, 2-(2-ethoxyethoxy)ethyl,
2-(2-methoxyethoxy)ethyl, 2-cyanoethyl, 2-(cyanoethoxy)ethyl, 4-(2-cyano-
ethoxy)butyl, 2-ethylhexyl, benzyl, phenylethyl. 3-phenylpropyl, phenoxy-
ethyl and furfuryl. Suitable branched radicals R5 include preferably those
having a methyl side chain, such as: isobutyl, tert-butyl, isopentyl,
1-methoxy-2-propanol and 1-ethoxy-2-propanol.
Examples of suitable radicals R include the following: methyl, ethyl,
n-propyl, isopropyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
n-decyl, 2-ethylhexyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl,
3-ethoxypropyl, 3-butoxypropyl, 3-phenoxypropyl, 3-(2-phenoxyethoxy)-
propyl, cyclohexyl, cyclohexylmethyl, benzyl and 2-phenylethyl.

Preferred dyes of the formula (I) are those in which R1 and R2
independently of one another are hydrogen, CI, Br, methyl, ethyl, n-
propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, uninterrupted
C1-C10 alkoxy or C1-C10 alkoxy interrupted by 1 to 2 oxygens;

unsubstituted or substituted phenoxy, CF3 or a di(C1-C4)-alkylamino group,
R3 and R4 have the definition of R1 and R2 or together with the ring carbon

atoms form a fused benzene ring, R5 is a C1-C12 alkyl which is
unsubstituted or substituted by CI, by CN or by unsubstituted or
substituted phenoxy and is uninterrupted or interrupted by 1 to 2
oxygen atoms, or is C6-C10 aryl-C1-C10 alkyl or hetarylalkyl, R6 is a
saturated or unsaturated C1-C12 alkyl which is unsubstituted or substituted
by unsubstituted or substituted phenoxy and is uninterrupted or interrupted
by 1 to 2 oxygens, and the ring D is unsubstituted or substituted by CN,
halogen atoms, in particular 1 to 4 CI atoms, 1 to 2 C1-C10 alkyl radicals
and/or 1 to 2 C1-C10 alkoxy radicals, or an unsubstituted or substituted
phenyl radical. In particular, however, the ring D is unsubstituted.
Particularly preferred dyes of the formula (I) are those of the formula (II)

in which R1 to R5 are as defined above, R1 to R4 independently of one
another preferably being hydrogen, chloro, methyl, ethyl, isopropyl, tert-
butyl, cyclohexyl, methoxy, ethoxy, n-propoxy, n-butoxy,
methoxyethyl, ethoxyethyl, butoxyethyl or phenoxy and
R5 preferably being n-butyl, isobutyl, n- or isopentyl, hexyl, octyl, 2-ethyl-
hexyl, methoxyethyl, ethoxyethyl, butoxyethyl, butoxyethoxyethyl.
Further preference is given to dyes of the formula (I) that conform to the
formula (III)

methyl, isopropyl, tert-butyl, cyclohexyl, methoxy, ethoxy, n-propoxy,
n-butoxy, methoxyethyl, ethoxyethyl, butoxyethyl or phenoxy and
R preferably being methyl, ethyl, propyl, isopropyl, allyl, n-butyl, isobutyl,
n- or isopentyl, hexyl, octyl, 2-ethylhexyl, cyclohexyl, methoxypropyl,
ethoxypropyl, 2-phenoxyethyl, 3-phenoxypropyl, 2-phenoxyethoxypropyl,
phenylethyl.
Besides the dye the printing inks contain 0.1% to 20% of dispersants.
Examples of suitable dispersants include sulfonated and sulfomethylated
lignins, formaldehyde condensates of aromatic sulfonic acids, formal-
dehyde condensates of unsubstituted or substituted phenol derivatives,
polyacrylates and their copolymers, polyethers containing styrene oxide,
modified polyurethanes, reaction products of alkylene oxides with
alkylatable compounds such as, for example, fatty alcohols, fatty amines,
fatty acids, carboxamides, resin acids and also unsubstituted or substituted
phenols.
For the inks to be used in the continuous flow process a conductivity of 0.5
to 25 mS/cm can be set by adding electrolyte. Examples of suitable
electrolytes include the following: lithium nitrate or potassium nitrate.
The dye inks of the invention may include organic solvents with a total
content of 1-60%, preferably of 5-40% by weight. Examples of suitable
organic solvents are
alcohols, e.g., methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, tert-
butanol, 1-pentanol, benzyl alcohol, 2-butoxyethanol, 2-(2-methoxy-
ethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol,
2-(2-propoxyethoxy)ethanol;
polyhydric alcohols, e.g.: 1,2-ethanediol, 1,2,3-propanetriol, 1,2-butanediol,
1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol,
1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol,
1,2-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,2-octanediol,
trimethylolethane, trimethylolpropane;
polyalkylene alcohols, e.g.: polyethylene glycol and polypropylene glycol
and their copolymers, alkylene glycols having 2 to 8 alkylene groups and
also corresponding thioether compounds, e.g.: monoethylene glycol,
diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol,
thiodiglycol, butyl diglycol, butyl triglycol, hexylene glycol, propylene glycol,
dipropylene glycol, tripropylene glycol;

The textile substrate is pretreated prior to printing with thickeners, which
prevent the motifs running when the printing ink is applied; examples of
such thickeners include sodium alginates, modified polyacrylates or highly
etherified galactomannans; and/or with substances which increase the
fixing yield.
These pretreatment reagents are applied uniformly to the textile substrate
in a defined amount using suitable applicators, such as with a 2- or 3-roll
padder, for example, with contactless spray technologies, by means of
foam application, or with appropriately adapted inkjet technologies, and
then dried.
After the textile fiber material has been printed it can be dried at 80 to
150°C and/or subsequently fixed. The fixing of the inkjet prints prepared
with disperse dyes takes place at elevated temperature, using saturated
steam, using superheated steam, using hot air, using compressed steam,
using microwaves, using infrared radiation, using laser or electron beams,
or using other suitable energy transfer techniques.
Fixing may be followed by a print aftertreatment, which leads to an
improvement in fastness properties and also to an immaculate white
ground.
Particularly on synthetic fiber materials the prints prepared with the dye
inks of the invention possess high color strength, good cold and hot
lightfastness, very good wetfastness properties, such as fastness to
washing, water, saltwater, weather fastness and perspiration fastness, and
also good fastness to heat setting and pleating, and crock fastness.
The examples which follow serve to illustrate the invention. Parts and
percentages are by weight unless otherwise noted. The relationship
between parts by weight and parts by volume is that of the kilogram to the
liter.
General procedure:
Preparation of an ink paste (containing 25% of dye): 125 g of dye are
combined together with X weight equivalents (1 weight equivalent

corresponds to 125 g) of dispersant/dispersant mixture and 375-125X g of
demineralized water and the mixture is milled in an agitated ball mill so that
the mean particle size is than 1 urn. It is possible for further additives such as biocides, defoamers,
etc. and also parts of the organic solvents used to be added even at the ink
paste milling stage.
The other constituents of the ink (organic solvents, other additives, water)
are added to the ink paste thus prepared (containing 25% of dye) and the
components are combined thoroughly by beating in a dissolver. Once they
have been filtered through a standard commercial filter paper (Macherey-
Nagel MN-614) the inks are ready for use.
Example 1
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
3.5% of the dye (1)

2.5% of dispersant Disperbyk 190
30% of 1,5-pentanediol
5% of diethylene glycol monomethyl ether
0.01% of biocide Mergal K9N
58.99% of water
using a drop-on-demand (piezo) inkjet printing head. The print is fully dried.
Fixing takes place by means of superheated steam at 175°C for 7 minutes.
The print is then subjected to an alkalinically reductive aftertreatment,
rinsed warm and then dried.
Example 2

A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
2% of the dye (2)

1 % of dispersant Tego Dispers 740 W
20% of glycerol
0.01% of biocide Mergal K9N
76.99% of water
using a drop-on-demand (bubblejet) inkjet printing head. The print is fully
dried. Fixing takes place by means of superheated steam at 175°C for
7 minutes. The print is then subjected to an alkalinically reductive
aftertreatment, rinsed warm and then dried. This gives a yellow-orange
print of high brightness having an outstanding durability and hot
lightfastness properties.
Example 3
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
7% of the dye (2)
3% of dispersant Tamol
30% of diethylene glycol
0.01% of biocide Mergal K9N

59.99% of water
using a drop-on-demand (piezo) inkjet printing head. The print is fully dried.
Fixing takes place by means of superheated steam at 175°C for 7 minutes.
The print is then subjected to an alkalinically reductive aftertreatment,
rinsed warm and then dried. This gives a yellow-orange print of high
brightness having an outstanding durability and hot lightfastness properties.
Example 4
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
1% of the dye (2)
0.6% of dispersant Tego Dispers 760 W
15% of polyethylene glycol 400
0.01% of biocide Mergal K9N
83.39% of water
using a drop-on-demand (bubblejet) inkjet printing head. The print is fully
dried. Fixing takes place by means of superheated steam at 175°C for
7 minutes. The print is then subjected to an alkalinically reductive
aftertreatment, rinsed warm and then dried. This gives a yellow-orange
print of high brightness having an outstanding durability and hot
lightfastness properties.
Example 5
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
5% of the dye (2)
2% of dispersant Ultrazine NA (ligninsulfonate, borregaard)
15% of polyethylene glycol 400
0.01% of biocide Mergal K9N
77.99% of water
using a drop-on-demand (piezo) inkjet printing head. The print is fully dried.

Fixing takes place by means of superheated steam at 175°C for 7 minutes.
The print is then subjected to an alkalinically reductive aftertreatment,
rinsed warm and then dried. This gives a yellow-orange print of high
brightness having an outstanding durability and hot lightfastness properties.
Example 6
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
4% of the dye (2)
1% of dispersant Ultrazine NA (ligninsulfonate, borregaard)
1% of dispersant Tego Dispers 650
0.01% of biocide Mergal K9N
83.99% of water
using a drop-on-demand (flatjet) inkjet printing head. The print is fully dried.
Fixing takes place by means of superheated steam at 175°C for 7 minutes.
The print is then subjected to an alkalinically reductive aftertreatment,
rinsed warm and then dried. This gives a yellow-orange print of high
brightness having an outstanding durability and hot lightfastness properties.
Example 7
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
3% of the dye (3)

3% of dispersant Disperbyk 190

10% of polyethylene glycol 400
20% of polypropylene glycol
0.01% of biocide Mergal K9N
63.99% of water
using a drop-on-demand (piezo) inkjet printing head. The print is fully dried.
Fixing takes place by means of superheated steam at 175°C for 7 minutes.
The print is then subjected to an alkalinically reductive aftertreatment,
rinsed warm and then dried. This gives a yellow-orange print of high
brightness having an outstanding durability and hot lightfastness properties.
Example 8
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
9% of the dye (3)
3% of dispersant Tego Dispers 740 W
5% of polyethylene glycol 200
10% of ethylene glycol
0.01% of biocide Mergal K9N
72.99% of water
using a drop-on-demand (piezo) inkjet printing head. The print is fully dried.
Fixing takes place by means of superheated steam at 175°C for 7 minutes.
The print is then subjected to an alkalinically reductive aftertreatment,
rinsed warm and then dried. This gives a yellow-orange print of high
brightness having an outstanding durability and hot lightfastness properties.
Example 9
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
5% of the dye (4)

5% of dispersant Tamol
10% of 1,2-hexanediol
20% of N-methylpyrrolidone
0.01% of biocide Mergal K9N
59.99% of water
using a drop-on-demand (bubblejet) inkjet printing head. The print is fully
dried. Fixing takes place by means of superheated steam at 175°C for
7 minutes. The print is then subjected to an alkalinically reductive
aftertreatment, rinsed warm and then dried. This gives a yellow-orange
print of high brightness having an outstanding durability and hot
lightfastness properties.
Example 10
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
2% of the dye (3)
2% of the dye (4)
2% of dispersant Ultrazine NA (ligninsulfonate, borregaard)
10% of diethylene glycol
20% of sulfolane
2% of urea
0.01% of biocide Mergal K9N
61.99% of water
using a drop-on-demand (bubblejet) inkjet printing head. The print is fully
dried. Fixing takes place by means of superheated steam at 175°C for
7 minutes. The print is then subjected to an alkalinically reductive
aftertreatment, rinsed warm and then dried. This gives a yellow-orange
print of high brightness having an outstanding durability and hot

lightfastness properties.
Example 11
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
1.5%of the dye(3)
2.5% of the dye (4)
2% of dispersant Tego Dispers 760 W
0.5% of dispersant Tego Dispers 650
20% of glycerol
5% of diethylene glycol
0.2% of Surfynol 104 E (Air Products)
0.01% of biocide Mergal K9N
68.29% of water
using a drop-on-demand (piezo) inkjet printing head. The print is fully dried.
Fixing takes place by means of superheated steam at 175°C for 7 minutes.
The print is then subjected to an alkalinically reductive aftertreatment,
rinsed warm and then dried. This gives a yellow-orange print of high
brightness having an outstanding durability and hot lightfastness properties.
Example 12
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
3% of the dye (5)

2% of dispersant Ultrazine NA (ligninsulfonate, borregaard)

15% of propylene glycol
5% of polyethylene glycol 800
0.01% of biocide Mergal K9N
74.99% of water
using a drop-on-demand (valvejet) inkjet printing head. The print is fully
dried. Fixing takes place by means of superheated steam at 175°C for
7 minutes. The print is then subjected to an alkalinically reductive
aftertreatment, rinsed warm and then dried. This gives a yellow, fluorescent
print of high brightness having an outstanding durability and hot
lightfastness properties.
Example 13
A textile fabric consisting of polyester is padded with a liquor consisting of
50 g/l of an 8% strength sodium alginate solution, 100 g/l of an 8-12%
strength bean gum ether solution and 5 g/l of monosodium phosphate in
water and then dried. The liquor pickup is 70%. The textile thus pretreated
is then printed with an aqueous ink prepared in accordance with the
procedure described above and containing
6% of the dye (6)

1.5% of dispersant Disperbyk 190
10% of 2-propanol
20% of polyethylene glycol 200
0.01% of biocide Mergal K9N
62.49% of water
using a drop-on-demand (piezo) inkjet printing head. The print is fully dried.
Fixing takes place by means of superheated steam at 175°C for 7 minutes.
The print is then subjected to an alkalinically reductive aftertreatment,
rinsed warm and then dried. This gives an orange print of high brightness
having an outstanding durability and hot lightfastness properties.

WE CLAIM
1. An aqueous printing ink for textile printing by the inkjet process, comprising one or
more dyes of the formula (I)

in which
A is N or a cyanomethylene radical,
B is a radical of the formula C(CN)COOR5 or N-R6,
R1 to R4 independently of one another are hydrogen, halogen, unsubstituted or
substituted C1-C8 alkyl or C5-C6 cycloalkyl, uninterrupted or oxygen-
interrupted C1-C10 alkoxy, unsubstituted or substituted C6-C10 aryloxy, CF3,
or unsubstituted or substituted dialkylamine, or pairs of adjacent R1 to R4
radicals together with the aromatic ring carbon atoms form a fused benzene
or naphthalene ring, which where appropriate is substituted further,
R5 is an unsubstituted or substituted and uninterrupted or oxygen-interrupted,
saturated or unsaturated C1-C20 alkyl radical, C6-C10 aryl C1-C10 alkyl or
hetarylalkyl,
R6 is unsubstituted or substituted and uninterrupted or oxygen-interrupted C1-C20
alkyl, cycloalkyl, cycloalkylalkyl or aralkyl, and
the ring D is unsubstituted or carries at least one substituent which where
appropriate, together with a further substituent in ortho position and the ring
carbon atoms, forms a fused benzene or naphthalene ring.
2. An aqueous printing ink for textile printing by the inkjet process, comprising dyes
of the formula (I) as claimed in claim 1, wherein R1 and R2 independently of one
another are hydrogen, CI, Br, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
tert-butyl, cyclohexyl, uninterrupted C1-C10 alkoxy or C1-C10 alkoxy

interrupted by 1 to 2 oxygens; unsubstituted or substituted phenoxy, CF3 or a
di(C1-C4)-alkylamino group,
R3 and R4 have the definition of R1 and R2 or together with the ring carbon atoms
form a fused benzene ring,
R5 is a C1-C12 alkyl which is unsubstituted or substituted by CI, by CN or by
unsubstituted or substituted phenoxy and is uninterrupted or interrupted by 1 to 2
oxygen atoms, or is C6-C10 aryl-C1-C10 alkyl or hetarylalkyl,
R6 is a saturated or unsaturated C1-C12 alkyl which is unsubstituted or substituted
by unsubstituted or substituted phenoxy and is uninterrupted or interrupted by 1
to 2 oxygens, and
ring D is unsubstituted or substituted by CN, halogen atoms, in particular 1 to 4 CI
atoms, 1 to 2 C1-C10 alkyl radicals and/or 1 to 2 C1-C10 alkoxy radicals, or a phenyl
radical, which are each uninterrupted or interrupted by 1 to 2 oxygen atoms.
3. An aqueous printing ink for textile printing by the inkjet process, comprising dyes
as claimed in claim 1 of the formula (II)

wherein R1 to R5 are as defined in claim 1.
4. An aqueous printing ink for textile printing by the inkjet process, comprising dyes
as claimed in claim 1 of the formula (III)

wherein R1 to R5 are as defined in claim 1.
5. An aqueous printing ink for textile printing by the inkjet process, comprising dyes
as claimed in claim 1 of the formula (IV)

wherein R1 to R4 and R6 are as defined in claim 1.
6. An aqueous printing ink for textile printing by the inkjet process, comprising dyes
as claimed in claim 1 of the formula (V)

wherein R1 to R4 and R6 are as defined in claim 1.
7. An aqueous printing ink for textile printing by the inkjet process as claimed in at
least one of claims 1 to 6, comprising one or more disperse dyes of the formula (I)
in amounts of 0.01% by weight to 40% by weight, based on the total weight of
the ink,
8. An aqueous printing ink for textile printing by the inkjet process as claimed in at
least one of claims 1-7, containing 0.1%-20% by weight of a dispersant and also
1% to 60% of organic solvents, based on the total weight of the ink.

9. A method of printing textile fiber materials by the inkjet process, which comprises
employing a printing ink as claimed in at least one of claims 1 to 8.

ABSTRACT

TITLE : HIGHLIGHT FASTNESS INKS FOR DIGITAL TEXTILE PRINTING

Disclosed are aqueous printing inks that are used for inkjet textile printing and contain
one of several compounds of general formula (I), wherein A,B, R1 to R6, and D have the
meaning indicated in claim 1, methods for the production thereof, and the use thereof
for inkjet textile printing.

HIGH-LIGHT FASTNESS INKS FOR DIGITAL TEXTILE PRINTING

Documents:

Inventors:

PCT Conventions: