Title of Invention	"RED REACTIVE DYES, THEIR PREPARATION AND THEIR USE"
Abstract	Reactive dyes of formula (1) wherein R<sb>1</sb> and R<sb>2</sb> independently of one another are hydrogen or unsubstituted or substituted C<sb>1</sb>- C<sb>4</sb>alkyl, D is a radical of a diazo component of the formula (2a) or (2b) X<sb>1</sb> and X<sb>2</sb> independently of one another are halogen, T is a fibre-reactive radical of the formula (3a) -NH-(CH<sb>2</sb>)<sb>2-3</sb>-SO<sb>2</sb>-Z, (3b) -NH-(CH<sb>2</sb>)<sb>2-3</sb>-O-(CH<sb>2</sb>)<sb>2-3</sb>-SO<sb>2</...

Title of Invention

"RED REACTIVE DYES, THEIR PREPARATION AND THEIR USE"

Abstract

Reactive dyes of formula (1) wherein R<sb>1</sb> and R<sb>2</sb> independently of one another are hydrogen or unsubstituted or substituted C<sb>1</sb>- C<sb>4</sb>alkyl, D is a radical of a diazo component of the formula (2a) or (2b) X<sb>1</sb> and X<sb>2</sb> independently of one another are halogen, T is a fibre-reactive radical of the formula (3a) -NH-(CH<sb>2</sb>)<sb>2-3</sb>-SO<sb>2</sb>-Z, (3b) -NH-(CH<sb>2</sb>)<sb>2-3</sb>-O-(CH<sb>2</sb>)<sb>2-3</sb>-SO<sb>2</...

Full Text	Red reactiye dyes, their preparation and their use The present invention relates to novel reactive dyes, to a process for their preparation and to their use in the dyeing or printing of textile fibre matenals The practice of dyeing using reactive dyes has recently led to higher demands being made on the quality of the dyeings and the economic efficiency of the dyeing process. As a result, there continues to ise a need for novel reactive dyes having improved properties, especially in respect of their application Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same time have good ease of washing off of unfixed dye They should also have a good colour yield and high reactivity, the objective being to provide especially dyeings havirig high degrees of fixing and good fastness properties The known dyes do not satisfy those requirements in all properties The dyes known from US-A-5,599,911 still have certain disadvantages in terms of the required properties The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel improved reactive dyes having the qualities charactensed above to a high degree. The novel dyes should especially be distinguished by high fixing yields and high fibre-dye binding stabilities The dyes should also yield dyeings having good allround fatness properties, for example fastness to light and to wetting It has been found that the problem posed is largely solved by the novel dyes defined herein-below The present invention accordingly relates to reactive dyes of formula (Formula Removed) wherein R1 and R2 independently of one another are hydrogen or unsubstituted or substitured C1- C4alkyl, D is a radical of a disazo component of the formula (Formula Removed) X1 and X2 independently of one another are halogen, T is a fibre-reactive radical of the formula (Formula Removed)………3a to 3g (R3)0-2 denotes from 0 to 2 identical or different substituents from the group hatogen, C1-C4alkyl, C1-C4alkoxy and sulfo, Z is vinyl or a -CH2-CH2-U radical and U is a group that is removable under alkaline conditions, Q is a -CH(Hal)-CH2-Hal or -C(Hal)=CH2 group, Hal is halogen, n is the number 0, 1 or 2, and m and q are indep^idently of one another the number 0 or 1 In the radical of formula (3c), Me is the methyl radical and Et the ethyl radical The said radicals are, in addkion to hydrogen, suitable as substituents on the nitrogen atom As C1-C4alkyl there comes into consideration for R1 and R2, each independently of any other(s) for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or isobutyl. The mentioned radicals may be unsubstituted or substituted, for example, by hydroxy, sulfo, sulfate, cyano, carboxy, C1-C4alkoxy or by phenyl, preferably by hydroxy, sulfate, C1-C4alkoxy or by phenyl. The corresponding unsubstituted radicals, especially methyl or ethyl, are preferred. As C1-C4alkyl there comes into consideration for R3, for example, methyl, ethyl, n-propyl, isopropyi, n-butyl, sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyl and especially methyl. As C1-C4alkoxy there comes into consideration for R3, for example, methoxy, ethoxy, n-propoxy, (sopropoxy, n-butoxy or isobutoxy, preferably methoxy or ethoxy and especially methoxy. As halogen there comes into consideration for R3, for example, fiuorine. chlorine or bromine, preferably chlorine or bromine and especially chlorine Preferably D is a radical of the formula (2b), wherein q is as defined above. R1 is preferably hydrogen R2 is preferably methyl or hydrogen, especially preferably hydrogen Preferably, (R3)0-2 ctenotes from 0 to 2 identical or different substrtuents from the group C1-C4alkyl, C1-C4alkoxy and sulfo, especially methyl, methoxy and sulfo. Rs is especially prerably hydrogen. X1 and X2 each independently of any other{s) are, for example, fluonne, chlorine or bromine, preferably fluorine or chlorine and especially chlorine T is preferably a radioil of formula {3c) or (3e), especially of formula (3c) Hal in the fibre-reactive radical of formula (3g) is preferably chionne or bromine, especially bromine. As leaving group U there comes into consideration, for example, -CI, -Br, -F, -OSO3H, -SSO3H, -OCO-CH3, -OPO3H2, -OCO-C6H5, -OSO2-C1-C4alkyl or -OSO2-N(C1-C4alkyl)2. Preferably, U is a group of formula -CI, -OSO3H. -SSO3H, -OCO-CH3. -OCO-C6H5 or -OPO3H2, especially -CI or -OSO3H Examples of suitable radicals Z are accordingly vinyl, ß-bromo- or ß-chloroethyl, ß-cetoxyethyl, ß-benzoyloxyethyl, ß-phosphatoethyl, ß-sutfatoethyl and ß-thio$ulfatoethyt. Z is preferably vinyl. ß-chlorc«thyl or ß-suifatoethyl Preferably, m is the number 1. Preferably, n is the number 1. Preferably, q is the number 0. The radical of formula (3c) is preferably a radical of formula (Formula Removed) especially preferaWy (3c') or (3c"), wherein Z has the definitions and prefen-ed meanings given above Preference is given to reactive dyes of formula (Formula Removed) wherein D, X1, X2, T and m each have the definitions and preferred meanings given above and, especially D is a radical of the formula (2b), wherein q is the number 0 or 1, preferably the number 0, X1 and X2 are chlorine, T is a radical of the above formula (3c), preferably (3c') or (3c"), Z is vinyl, ß-sulfatoethyl or ß-chloroethyl, preferably vinyl or ß-sulfatoethyl, and m is the number 1. The dyes according to the invention are prepared by reacting with one another, in a suitable order, the compounds of formulae (Formula Removed)……………4 to 10 wherein D, R1, R2, Xi, X2, T, m and n each have the definitions and preferred meanings given hereinabove, by condensation, diazotation and coupling reactions. Preferably equimolar amounts, such as approximately one molar equivalent each of the compounds of formulae (4), (5), (6), (7). (8), (9) and (10) are used. A suitable 2,4,6-Trihalo-s-triazin (cyanuric halide) of formula (7) or (10) is 2,4,6-Trichloro-s-trtazin (cyanuric chloride) or 2,4.6-Trifluoro-s-triazin (cyanuric fluoride), especially cyanuric chloride. Since the above compounds can be reacted with one another in different orders, and also, optionally, can be reacted with one another simultaneously, vanous process variants are possjble. In general, the reaction is carried out stepwise, the order in which the single reactions between the individual reactants are carried out advantageously bemg governed by tfie particular conditions. In a preferred embodiment, (t) approximately one molar equivalent of a compound of formula (8) is condensed with s^proximately one molar equivalent of a compound of fonnuia (10) to form a compound of formula (Formula Removed)……………11 (ii) approximately one molar equivalent of a compound of formula (11) obtained according to (i) is reacted with approximately one molar equivalent of a compound of formula (9) to form a secondary condensation product of formula (Formula Removed)…………… 12 (ill) approximately one molar equivalent of a compound of formula (5) is condensed with approximately one molar equivalent of a compound of formula (7) to form a compound of formula (Formula Removed)…………… 13 (iv) approximately one molar equivalent of a compound of formula (13) obtained according to (iii) is reacted withapproximately one molar equivalent of a compound of formula (6) to form a secondary condensation product of formula (Formula Removed)…………… 14 (V) approximately one molar equivalent of a compound of formula (4) is diazotised and coupled to approximsrtely one molar equivalent of a compound of formula (14) obtained according to (iv) to form a product of formula (Formula Removed)…………… 15 (vi) approximately one molar equivalent of a compound of formula (15) obtained according to (v) is diazotised and coupled to approximately one molar equivalent of a compound of formula (12) obtair»d according to (ii) to form a reactive dye of formula (1) According to another embodiment, an azo compound of formula (Formula Removed)……………16 may be prepared in advance by diazotizing approximately one molar equivalent of a compound of formula (4) and coupling to approximately one molar equivalent of a compound of formula (5) and proceeding in accordance to (111), wherein one molar equivalent of a compound of formula (16) is used instead of one molar equivalent of a compound of formula (5), (iv) and (vi) above Dtazotisatbn and coi.^ling are earned out in customary manner, for example by diazotising the compound of formula (4) or the compound of formula (15) in mineral acid solution, for example hydrochloric acid solution, with a nitrite, for example sodium nitrite, at low temperature, for example, at from 0 to 5°C in the case of the compound of formula (4) or at from 10 to 30°C In the case of the compound of formula (15), and then coupling with the awresponding coupling component in neutral to slightly acidic medium, for example at pH from 3 to 7.5, preferably from 3 to 4 or from 6 to 7.5, and at low to moderate temperatures, for example from 0 to 30°C. The condensation reactions are generally carried out analogously to known methods, usually in aqueous solution at temperatures of, for example, from 0 to 30°C and a pH value of, for example, from 2 to 10. The compounds of formulae (4), (5), (6), (7), (8), (9) and (10) are known or carj be prepared analogously to known compounds. The reactive dyes of formula (1) contain sulfo groups, which are each either in the form of the free sulfo acid or, preferably, In the form of a salt thereof, for example a sodium, lithium, potassium or ammonium salt, or a salt of an organic amine, for example a triethanol-ammonium salt. TTie reactive dyes of formula (1) may comprise further additives, for example sodium chloride or dextrin The reactive dyes of formula (1) according to the invention may optionally concise further adjuvants which, for examjf^e, improve handling or increase storage stability, such as, for example, buffers, dispersants or anti-dusts. Such adjuvants are known to the person skilled in the art. The dyes of formula (1) according to the invention are suitable for dyeing and printing an extremely wide variety of materials, such as hydroxyl-grouß-containing or nitrc^en-containing frtjre materials. Examples that may be mentioned are silk, leather, wool, polyamide fibres and polyurethanes, and especially cellulosic fibre materials of all kinds. Such cellulosic fibre n^terials &re, for examfie, natural cellulosic fibres, such as cotton, linen and hemp, and also cellulose and regenerated cellulose. The dyes according to the invention are sAso suitable for dyeing or printing l^cfc'oxyl-grouß-containing fibres present in blend fabncs, e.g. trfends of cotton with polyester fibres or polyamide fibres. The dyes according to the invention are especially suitable for dyeing or printing celluiosic, especially cotton-containing, fibre materials. They can furthermore be used in the dyeing or printing of natural or synthetic polyamide fibre materials The presait invention accordingly relates also to the use of the dyes of formula (1) according to the invention in the dyeing or printing of hydroxyl-grouß-containing or nitrogen-containing, especially celluiosic, fibre materials The dyes of formula (1) according to the invention can be applied to the fibre matenal and fixed to the fibre in a variety of ways, especially in the form of aqueous dye solutions and print pastes. They are suitable both for the exhaust method and for dyeing in accordance with the pad-dyeing method, according to which the goods are impregnated with aqueous, optionally salt-contati^ng, dye solutions and, after treatment with alkali or in tte presence of alkali, the dyes are fixed, where appropnate with the action of heat or by stonrag for several hours at room temperature. After fixing, the dyeings or pnnts are rinsed thoroughly with cold and hot water, optjor>aHy with the addition of an agent that has a dispersing action and promotes the diffusion of unfixed dye The dyes accordir^ to the invention are distinguished by high reactivity, good fixing ability £Mid a very good buiid-up behaviour. They can accordingly be used in accordance with the ffichaust dyeing method at low dyeing temperatures and require only short st^iming times in the pad-steam m^hod. The degrees of fixing are high and unfixed dye can be washed off easily, the difference between the degree of exhaust and the degree of fixing being remarkaWy small, that is to say the soaping loss being very low The dyes according to the invention are also suitable especially for printing, more especially on cotton, twt are equally suitable also for pnnttng nitrogen-containing fibres, for example wool or silk or blend fabrics that comprise wool or silk The dyeings and prints produced using the dyes according to the invention have a high tinctorial strength and a high fil»re-to-dye binding stability in both the acidic and the alkaline range, and furthermore have good fastness to light and very good wet-fastness prof^rties, such as fastness to washing, to water, to sea water, to cross-dyeing and to perspiration, as well as good fastness to pleating, to ironing and to rubbing The dyeings obtained exhibit fibre levelness and surface levelness The dyes of formula (1) according to the invention are also suitable as colorants for use in recording systems. Suitable recording systems are, for example, commercially available ink-jet printers for paper or textile printing, or wnting instruments, such as fountain pens or ballpoint pens, and especially ink-jet printers For that purpose, the dyes accwding to the invention are first of ail brought into a form suitable for use in recording systems. A suitable form is, for exampte, an aqueous ink, which comprises the dyes according to tie invention as colorants. The inks can be prepared in customary manner by mixing together the individual components in the desired amount of water As substrates there come into consideration the above-mentioned hydroxyl-group-containing or nitrogen-containir^ filwre materials, especially cellulosic fibre materials. The fibre materials are preferably textte fibre matenals Substrates that also come into consideration are paper and plastics films As examples of paper there may be mentioned commercially available ink-jet paper, photo paper, glc^sy paper, plastics-coated paper, e.g. Epson Ink-jet Paper, Epson PhcAo Paper, Epson Glossy Paper, Epson Glossy Film, HP Special Ink-jet Paper, Encad Photo Gloss Paper and llford Photo Paper. Plastics films are, for example, transparent or doudy/opaque. Suitable plastics films are, for example, 3M Transparency Film. Depending on the nature of the use, for example textile printing or paper pnntirig, it may be necessary, for example, for the viscosity or other physical properties of the ink, especially properties that have an influence on the affinity for the substrate in question, to be adapted accordingly. The dyes used in the aqueous inks should preferably have a low salt content, that is to say they shoutel have a total content of salts of less than 0.5 % by weight, based on the weight of the dyes. Dyes that have relatively high salt contents as a result of their preparation and/or as a result of the sukBequent addition of diluents can be desalted, for example by membrane separation procedures, such as ultrafiltration, reverse osmosis or dialysis The inks preferably have a total content of dyes of from 1 to 35 % by weight, especially from 1 to 30 % by weight and preferably from 1 to 20 % by weight, based on the total weight of the ink. The preferred tower limit in this case is a limit of 1.5 % by weight, preferably 2 % by weight and especially 3 % by weight The inks may compsise water-mlscible organic solvents, for example C1-C4alcohols, e g. nrwBthanol, ethanol, n-prqjanol, isopropanol, n-butanol, sec-butanol, tert-butanol or iso-butanol, amides, e.g. dimethytformamide or dimethylacetamide, ketones or kelone alcohols, e.g. acetone or diacetone ala)hol; ethers, e g. tetrahydrofuran or dioxane. nitrogen-containing heterocyclic ajmfwunds, e.g N-methyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidone, polyaU$ylene glycols, e.g. polyethylene glycol or polypropylene glycol, C2-C6alkylene glycols and ttwoglycols, e.g ethylene glycol, propylene glycol, butytene glycol, triethylene glycol, thtoctigiycol, hexylene glycol and diethylene glycol, other polyols, e.g gfycerol or 1,2,6-haxanetriol; and C1-C4alkyl ethers of polyhydric alcohols, e.g. 2-methoxy-etianol, 2-(2-meth0xyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxy-e^oxy)ethoxy]ethanoi or 2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyi-2-pyrrolidone, diethylene glycol, glycerol or especially 1,2-propylene glycol, usually in an amount of from 2 to ^ % by weight, especially from 5 to 30 % by weight and preferably from 10 to 25 % by weight, based on the total weight of the ink. In addition, the inks may also comprise solubilisers, e.g. e-caprolactam The inks may comprise thickeners of natural or synthetic origin, inter alia for the purpose of adjusting the viscosity. Examples of thickenws that may be mentioned include commercially available alginate thickeners, starch ethers or tocust bean flour ethers, especially sodium alginate on its own or in admixture with modified cellutose, e.g methyl cellulose, ethyl cellulose, carljoxymethyi cellulose, hydroxyethyl cellutose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl meth^ cellulose, especially with preferably from 20 to 25 % by weight carboxymethyl celtolose. Synthetic thickeners that may be mentioned are, for example, those based on poly(metti)acrylic acids or poly(meth)acrylamides and also polyalkylene glycols having a molecular weigtit of, for example, from 2000 to 20 000, such as, for example. polyethylene glycol or polypropylene glycol or mixed polyalkylene glycols of etl^lene oxide and propylene oxide. The inks comprise such thickeners, for example, in an amount of from 0 01 to 2 % by weight, especially from 0.01 to 1 % by weight and preferably from 0 01 to 0 5 % by we^ht, based on the total weight of the ink The inks may also comprise buffer substances, e.g. borax, borates, phosphates, poly-phosphates or citraies. Examples that may be mentioned include borax, sodium borate, sodium tefraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate and sodium citrate. They are used especially in amounts of from 0.1 to 3 % by weight, preferably from 0 1 to 1 % by weight, based on the total weight of the ink, in order to establish a pH value of, for example, from 4 to 9, especially from 5 to 8.5 As further additives, the inks may compnse surfactants or humectants Suitable surfactants include commercially available anionic or non-ionic surfactants As humectants in the inks according to the invention there come into consideration, for example, wea or a mixture of sodium lactate (advantageously in the form of a 50 % to SO % aqueous solution) and glycerol and/or propylene glycol in amounts of preferably from 0.1 to 30 % by weight, especially from 2 to 30 % by weight Preference is given to Inks having a viscosity of from 1 to 40 mPa s, especially from 1 to 20 mPas and more especially from 1 to 10 mPa s Furthermore, the mks may in addition comprise customary additives, e.g. anti-foams or especially preservatives that inhibit fungal and/or bacterial growth Such additives are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the ink As preswvatives there come into consideration formaldehyde-yielding agents, for example paraformaldehyde and trioxane, especially aqueous, approximately from 30 to 40 % by weight formaldehyde solutions, imidazole compounds, for example 2-(4-thiazolyl)-benzimidazole, thiazoie compounds, for example 1,2-benzisothiazolin-3-one or 2-n-octyl- isothiazolin-3-one, iodine compounds, nitnles, phenols, haloalkylthio compounds or pyridine derivatives, especially 1,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-or*e A suitable preservative is, for example, a 20 % by weight solution of 1,2-benzisothiazolin-3-one in dipropylene glycol (Proxel® GXL). The inks may also comprise further additives, such as fluorinated polymers or telomers, for example polyethoxyperfluoroalcohols (Forafac® or Zonyl® products) in an amount of, for example, from 0.01 to 1 % by weight, based on the total weight of the ink In the case of the ink-jet pnnting method, individual droplets of ink are sprayed onto a substrate from a nozzle in a controlled manner. It is mainly the continuous ink-\|et method and the droß-on-demand method that are used for that purpose. In the case of the continuous ink-jet method, the droplets are produced continuously, droplets not required for the printing operation being discharged into a receptacle and recycled. In the case of the drop-on-ctemand method, on the other hand, droplets are generated as desired and used for printing, that is to say, droplets are generated only when required for the pnnting operation The production of the droplets can be effected, for example, by means of a piezo ink-jet head or by thermal energy (bubble jet). Preference is given to printing by means of a piezo ink-jet head and to printing according to the continuous ink-jet method The present inventfon accordingly relates also to aqueous inks that comprise the dyes of formula (1) according to the invention and to the use of such inks in an ink-jet pnnting method for printing a variety of substrates, especially textile fibre materials, the definitions and preferences indkated above applying to the dyes, the inks and the substrates. The follovwng Examfi^s serve to illustrate the invention Unless otherwise indicated, the temperatures are pven in degrees Celsius, parts are parts by weight and percentages relate to % by weight. Parts by weight relate to parts by volume in a ratio of kilograms to litres Example 1 • (a) 40 parts of a neufral solution of 1-amino-8-hydroxynaphthalene-3,6-disulfc»iic acid (H-acid) in 200 parts of water are added drop wise at pH 2-2 5 and 0-5°C to a fine suspension of 23.5 parts of cyanuric chloride in 100 parts by volume of water and 100 parts of ice The mixture is adjusted to pH 2.5 by means of hydrochlonc acid. During the additicsi the reaction temperature is maintained at 0-5°C by cooling After the addition is finished the pH is maintained at pH 2 with a soda ash solution (20%) until the reaction is complete (b) A neutral soiution of 35 parts of 3-(ß-sulfatoethylsulfonyl)aniline in water is added to the reaction mixture oWaned according to (a) The pH is adjusted to 4.5-5 with a soda ash solution (20%) and maintained at these conditions. The temperature is nsing (5-25°C) until the reaction is complete The mixture obtained contains a compound which, in the form of the free acid, corresponds to formula (Formula Removed) (c) 31 parts of hydrochlonc acid (32%) are added to a neutral solution of 105 parts of the following intermediate (Formula Removed) in 4000 parts of water. 32 parts by volume of sodium nitrite 4 N are added drop wise at 20-30°C to this solution. An excess of sodium nitnte must be indicated by starch-iodide paper after the addition is finished. The reaction mass is stirred until diazotization is complete. Excess erf nitrite is then removed by addition of sulfamic acid (d) The diazo mi)^ure obtained according to (c) is dosed to the cooled mixture obtained according to (b) at 5 to 25'C maintaining the reaction mixture at pH 6 5-7.5 by means of sodium hydroxide solution. The resulting reaction mass is stirred until couplir^ is complete, desalinated by dialysis and dried by lyophitisation A dye is obtained as a powder (max = 518 nm) which, in the form of the free acid, corresponds to formula (Formula Removed)………………101 The dye prints or dyes cellulose in a briihant red shade with good fastness properties. Examples 2 to 9: Analogously to the procedure described in Example 1, the compounds of formulae (Formula Removed)……………… 102 to 109 (max = 514 nm) can be prepared, which likewise yield brilliant red shaded dyeings or prints on cellulose having good fastness properties. Dyeing procedure I X% (see Table 1 betow) of the dyestuff of formula (101) according to Example 1 or the dyestuff known in the art according to formula (110), respectively, are dissolved in 400 parts of water. To this solution are added 500 parts of a solution which contains Y gfl (see Table 1 below) of common salt (sodium chlonde). 100 paris of non-mercerized cotton tricot are introduced into the dye bath at 80°C. The temperature is maintained for 15 minutes and then increased to 90°C within 5 minutes. After 30 minutes at 90°C the temperature is decreased to 70°C within 10 minutes whereupon 100 parts of a solution containing Z1 g/l (see Table 1 below) of calcined sodium carbonate (soda ash) are added After 15 minutes at 70°C Z2 ml/1 (see Table 1 below) NaOH (36Be) are added. Dyeing is continued for a furth®r 30 minutes at this temperature. The dyed goods are then rinsed, soaped at the boil for a cfuarter of an hour with a non-ionic detergent, nnsed again and dried (Formula Removed)………………110 Table 1: Salt and Alkali Recommendations (Tabble Removed) Tabte 2: Build-up : dependence of reference depth (RP) from dyestuff concentration (Tabble Removed) Table 2 shows that build-up of the dyestuff of formula (101) according to Example 1 is superior to the build-up properttes of the dyestuff of formula (110) known in the art. Furthermore, washing-off properties of the dyestuff of formula (101) according to the present invention are improved with respect to the dyestuff of formula (110). Degree of fixation of the dyestuff of formula (101) according to the present invenntion is 75%, whereas the dyestuff of formula (110) known in the art shows a degree of fixation of only 66%. Dyeing procedure ll 100 parts of cotton fabric are introduced at 70°C into 1500 parts of a dye bath containing 20 g/l of sodium chloride and 2 parts of the reactive dye obtained according to Example 1. After 45 minutes at 70°C, 5 g/l of calcined soda and after additional 10 minutes 2 ml/I NaOH (36°Be) are added. Dyeing is continued for a further 45 minutes at that temperature. The dyed goods are then rinsed, soaped at the boil for a quarter of an hour with a non-ionic detergent, rinsed again and dried As an alternative to the above procedure, the dyeing can be carned out at 80°Cinstead of at 70°C Dyeing procedure III 0.1 part of the dye according to Example 1 is dissolved in 200 parts of water, and 0.5 part of sodium sulfate, 0 1 part of a leveling agent (based on the condensation produet of a higher aliphatic amine and ethylene oxide) and also 0 5 part of sodium acetate are added. The pH is then adjusted to a value of 5.5 using acetic acid (80 %). The dye bath is heated at 50°C for 10 minutes and then 10 parts of a woollen fabnc are added Heating is then carried out in the course of approximately 50 minutes to a temperature of 100°C and dyeing is carried out at that temperature for 60 minutes, after which the dye bath is allowed to cool to 90°C and the dyed goods are removed. The woollen fabnc is washed with hot and cold water and is then spun and dried Pnnting procedure I 3 parts of the dye obtained according to Example 1 are spnnkled, with rapid stirring, into 100 parts of a stock thickener containing 50 parts of 5 % sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium hydrogen carbonate The pnnt paste so obtained is used to print a cotton fabric, and the resulting printed matenal is dried and steamed in saturated steam for 2 minutes at 102°C. The printed fabric is then nnsed, if desired soaped at the boil and rinsed again, and subsequently dried. Printing procedure II (a) Mercensed cotton satin is pad-dyed with a liquor containing 30 g/1 of sodium carnonate and 50 g/1 of urea (70 % tiquor pick-up) and dried (b) Using a droß-on-demarnd ink-jet head (bubble jet), the cotton satin pretreated according to Step (a) is printed with an aqueous ink containing - 15 % by weight of the reactive dye of formula (101) according to Example 1, - 15 % by weight of 1,2-propylene glycol and - 70 % by weight of water The print is dried compietety and fixed in saturated steam for 8 minutes at 102°C, cold-rinsed, washed off at the boil, rinsed again and dned. We Claims :- 1. A reactive dye of formula (Formula Removed) wherein R1 and R2 independently of one another are hydrogen or unsubstituted or substituted C1- C4a!kyl, D is a radical of a diazo component of the formula (Formula Removed) X1 and X2 independently of one another are halogen, T is a fibre-reactive radical of the formula (Formula Removed)………..3a to 3g (R3)0-2 denotes from 0 to 2 identical or different substituents from the group halogen, C1-C4alkyl, C1-C4alkoxy and sulfo, Z is vinyl or a -CH2-CH2-U radical and U is a group that is removable under alkaline conditions, Q is a -CH(Hal)-CH2-Hal or -C(Hal}=CH2 group, Hal is halogen, n is the number 0,1 or 2, and m and q are independently of one another the number 0 or 1. 2. A reactive dye according to claim 1, wherein R1 and R2 are hydrogen. 3. A reactive dye according to either claim 1 or claim 2, wherein X1 and X2 indeperidently from one another are chloro or fluoro. 4. A reactive dye according to any one of claims 1 to 3, wherein Z is vinyl, ß-chloroethyl or ß-sulfatoethyi. 5. A reactive dye according to any one of claims 1 to 4 that corresponds to formula (Formula Removed) wherein D, X1, X2, T and m are each as defined in claim 1. 6. A reactive dye according to claim 5, wherein T is a radical of formula (Formula Removed) (R3)0-2 denotes from 0 to 2 identical or different substituents from the group nrpthyl, methoxy and sulfo, Z is vinyl, ß-chloroethyl or ß-sulfatoethyl, Me is the methyl radical and Et the ethyl radical, and m is the number 1. 7. A reactive dye according to either claim 5 or claim 6, wherein D is a radical of a diazo component of the formula (Formula Removed) X1 and X2 are chlorine, T is a radical of formula (Formula Removed) Z is vinyl or ß-sulfatoethyl, m is the number 1, and q is the number 0. 8. A process for the preparation of a reactive dye of formula (1) according to daim 1, which comprises reacting with one another, in a suitable order, the compounds of formulae (Formula Removed)……..4 to 10 wherein D, R1, R2, Xi, X2, T, n and m are each as defined in claim 1, by condensation, diazotation and coupling reactions. 9. The use of a readive dye according to any one of claims 1 to 7 or of a reactive dye prepared according to claim 8 in the dyeing or printing of hydroxyl-group-containing or nitrogen-containing fibre material. 10. Use according to claim 9, wherein cellulosic fibre material, especially cottpn-containing fibre material, is dyed or printed. 11. An aqueous ink that comprises a reactive dye of formula (1) according to claim 1. 12. A process for printing textile fibre material, paper or plastics film according to the ink-jet printing method, which comprises using an aqueous ink according to claim 11.

Full Text

Red reactiye dyes, their preparation and their use
The present invention relates to novel reactive dyes, to a process for their preparation and to their use in the dyeing or printing of textile fibre matenals
The practice of dyeing using reactive dyes has recently led to higher demands being made on the quality of the dyeings and the economic efficiency of the dyeing process. As a result, there continues to ise a need for novel reactive dyes having improved properties, especially in respect of their application
Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same time have good ease of washing off of unfixed dye They should also have a good colour yield and high reactivity, the objective being to provide especially dyeings havirig high degrees of fixing and good fastness properties The known dyes do not satisfy those requirements in all properties
The dyes known from US-A-5,599,911 still have certain disadvantages in terms of the required properties
The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel improved reactive dyes having the qualities charactensed above to a high degree. The novel dyes should especially be distinguished by high fixing yields and high fibre-dye binding stabilities The dyes should also yield dyeings having good allround fatness properties, for example fastness to light and to wetting
It has been found that the problem posed is largely solved by the novel dyes defined herein-below
The present invention accordingly relates to reactive dyes of formula
(Formula Removed)
wherein
R1 and R2 independently of one another are hydrogen or unsubstituted or substitured C1-
C4alkyl,
D is a radical of a disazo component of the formula

(Formula Removed)
X1 and X2 independently of one another are halogen, T is a fibre-reactive radical of the formula
(Formula Removed)………3a to 3g
(R3)0-2 denotes from 0 to 2 identical or different substituents from the group hatogen,
C1-C4alkyl, C1-C4alkoxy and sulfo,
Z is vinyl or a -CH2-CH2-U radical and U is a group that is removable under alkaline
conditions,
Q is a -CH(Hal)-CH2-Hal or -C(Hal)=CH2 group,
Hal is halogen,
n is the number 0, 1 or 2, and
m and q are indep^idently of one another the number 0 or 1
In the radical of formula (3c), Me is the methyl radical and Et the ethyl radical The said radicals are, in addkion to hydrogen, suitable as substituents on the nitrogen atom
As C1-C4alkyl there comes into consideration for R1 and R2, each independently of any other(s) for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or isobutyl. The mentioned radicals may be unsubstituted or substituted, for example, by hydroxy, sulfo, sulfate, cyano, carboxy, C1-C4alkoxy or by phenyl, preferably by hydroxy, sulfate, C1-C4alkoxy or by phenyl. The corresponding unsubstituted radicals, especially methyl or ethyl, are preferred.

As C1-C4alkyl there comes into consideration for R3, for example, methyl, ethyl, n-propyl, isopropyi, n-butyl, sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyl and especially methyl.
As C1-C4alkoxy there comes into consideration for R3, for example, methoxy, ethoxy, n-propoxy, (sopropoxy, n-butoxy or isobutoxy, preferably methoxy or ethoxy and especially methoxy.
As halogen there comes into consideration for R3, for example, fiuorine. chlorine or bromine, preferably chlorine or bromine and especially chlorine
Preferably D is a radical of the formula (2b), wherein q is as defined above.
R1 is preferably hydrogen
R2 is preferably methyl or hydrogen, especially preferably hydrogen
Preferably, (R3)0-2 ctenotes from 0 to 2 identical or different substrtuents from the group C1-C4alkyl, C1-C4alkoxy and sulfo, especially methyl, methoxy and sulfo.
Rs is especially prerably hydrogen.
X1 and X2 each independently of any other{s) are, for example, fluonne, chlorine or bromine, preferably fluorine or chlorine and especially chlorine
T is preferably a radioil of formula {3c) or (3e), especially of formula (3c)
Hal in the fibre-reactive radical of formula (3g) is preferably chionne or bromine, especially bromine.
As leaving group U there comes into consideration, for example, -CI, -Br, -F, -OSO3H, -SSO3H, -OCO-CH3, -OPO3H2, -OCO-C6H5, -OSO2-C1-C4alkyl or -OSO2-N(C1-C4alkyl)2. Preferably, U is a group of formula -CI, -OSO3H. -SSO3H, -OCO-CH3. -OCO-C6H5 or -OPO3H2, especially -CI or -OSO3H
Examples of suitable radicals Z are accordingly vinyl, ß-bromo- or ß-chloroethyl, ß-cetoxyethyl, ß-benzoyloxyethyl, ß-phosphatoethyl, ß-sutfatoethyl and ß-thio$ulfatoethyt.
Z is preferably vinyl. ß-chlorc«thyl or ß-suifatoethyl
Preferably, m is the number 1.
Preferably, n is the number 1.
Preferably, q is the number 0.
The radical of formula (3c) is preferably a radical of formula
(Formula Removed)
especially preferaWy (3c') or (3c"), wherein Z has the definitions and prefen-ed meanings given above
Preference is given to reactive dyes of formula
(Formula Removed)
wherein
D, X1, X2, T and m each have the definitions and preferred meanings given above and,
especially
D is a radical of the formula (2b), wherein q is the number 0 or 1, preferably the number 0,
X1 and X2 are chlorine,
T is a radical of the above formula (3c), preferably (3c') or (3c"),
Z is vinyl, ß-sulfatoethyl or ß-chloroethyl, preferably vinyl or ß-sulfatoethyl, and
m is the number 1.
The dyes according to the invention are prepared by reacting with one another, in a suitable order, the compounds of formulae
(Formula Removed)……………4 to 10
wherein D, R1, R2, Xi, X2, T, m and n each have the definitions and preferred meanings given hereinabove, by condensation, diazotation and coupling reactions.
Preferably equimolar amounts, such as approximately one molar equivalent each of the compounds of formulae (4), (5), (6), (7). (8), (9) and (10) are used.
A suitable 2,4,6-Trihalo-s-triazin (cyanuric halide) of formula (7) or (10) is 2,4,6-Trichloro-s-trtazin (cyanuric chloride) or 2,4.6-Trifluoro-s-triazin (cyanuric fluoride), especially cyanuric chloride.
Since the above compounds can be reacted with one another in different orders, and also, optionally, can be reacted with one another simultaneously, vanous process variants are possjble. In general, the reaction is carried out stepwise, the order in which the single reactions between the individual reactants are carried out advantageously bemg governed by tfie particular conditions. In a preferred embodiment,
(t) approximately one molar equivalent of a compound of formula (8) is condensed with s^proximately one molar equivalent of a compound of fonnuia (10) to form a compound of formula
(Formula Removed)……………11
(ii) approximately one molar equivalent of a compound of formula (11) obtained according to (i) is reacted with approximately one molar equivalent of a compound of formula (9) to form a secondary condensation product of formula
(Formula Removed)…………… 12
(ill) approximately one molar equivalent of a compound of formula (5) is condensed with approximately one molar equivalent of a compound of formula (7) to form a compound of formula
(Formula Removed)…………… 13
(iv) approximately one molar equivalent of a compound of formula (13) obtained according to (iii) is reacted withapproximately one molar equivalent of a compound of formula (6) to form a secondary condensation product of formula
(Formula Removed)…………… 14
(V) approximately one molar equivalent of a compound of formula (4) is diazotised and coupled to approximsrtely one molar equivalent of a compound of formula (14) obtained according to (iv) to form a product of formula

(Formula Removed)…………… 15
(vi) approximately one molar equivalent of a compound of formula (15) obtained according to (v) is diazotised and coupled to approximately one molar equivalent of a compound of formula (12) obtair»d according to (ii) to form a reactive dye of formula (1)
According to another embodiment, an azo compound of formula
(Formula Removed)……………16
may be prepared in advance by diazotizing approximately one molar equivalent of a compound of formula (4) and coupling to approximately one molar equivalent of a compound of formula (5) and proceeding in accordance to (111), wherein one molar equivalent of a compound of formula (16) is used instead of one molar equivalent of a compound of formula (5), (iv) and (vi) above
Dtazotisatbn and coi.^ling are earned out in customary manner, for example by diazotising the compound of formula (4) or the compound of formula (15) in mineral acid solution, for
example hydrochloric acid solution, with a nitrite, for example sodium nitrite, at low temperature, for example, at from 0 to 5°C in the case of the compound of formula (4) or at from 10 to 30°C In the case of the compound of formula (15), and then coupling with the awresponding coupling component in neutral to slightly acidic medium, for example at pH from 3 to 7.5, preferably from 3 to 4 or from 6 to 7.5, and at low to moderate temperatures, for example from 0 to 30°C.
The condensation reactions are generally carried out analogously to known methods, usually in aqueous solution at temperatures of, for example, from 0 to 30°C and a pH value of, for example, from 2 to 10.
The compounds of formulae (4), (5), (6), (7), (8), (9) and (10) are known or carj be prepared analogously to known compounds.
The reactive dyes of formula (1) contain sulfo groups, which are each either in the form of the free sulfo acid or, preferably, In the form of a salt thereof, for example a sodium, lithium, potassium or ammonium salt, or a salt of an organic amine, for example a triethanol-ammonium salt.
TTie reactive dyes of formula (1) may comprise further additives, for example sodium chloride or dextrin
The reactive dyes of formula (1) according to the invention may optionally concise further adjuvants which, for examjf^e, improve handling or increase storage stability, such as, for example, buffers, dispersants or anti-dusts. Such adjuvants are known to the person skilled in the art.
The dyes of formula (1) according to the invention are suitable for dyeing and printing an extremely wide variety of materials, such as hydroxyl-grouß-containing or nitrc^en-containing frtjre materials. Examples that may be mentioned are silk, leather, wool, polyamide fibres and polyurethanes, and especially cellulosic fibre materials of all kinds. Such cellulosic fibre n^terials &re, for examfie, natural cellulosic fibres, such as cotton, linen and hemp, and also cellulose and regenerated cellulose. The dyes according to the invention are sAso suitable for dyeing or printing l^cfc'oxyl-grouß-containing fibres present in blend fabncs, e.g. trfends of
cotton with polyester fibres or polyamide fibres. The dyes according to the invention are especially suitable for dyeing or printing celluiosic, especially cotton-containing, fibre materials. They can furthermore be used in the dyeing or printing of natural or synthetic polyamide fibre materials
The presait invention accordingly relates also to the use of the dyes of formula (1) according to the invention in the dyeing or printing of hydroxyl-grouß-containing or nitrogen-containing, especially celluiosic, fibre materials
The dyes of formula (1) according to the invention can be applied to the fibre matenal and fixed to the fibre in a variety of ways, especially in the form of aqueous dye solutions and print pastes. They are suitable both for the exhaust method and for dyeing in accordance with the pad-dyeing method, according to which the goods are impregnated with aqueous, optionally salt-contati^ng, dye solutions and, after treatment with alkali or in tte presence of alkali, the dyes are fixed, where appropnate with the action of heat or by stonrag for several hours at room temperature. After fixing, the dyeings or pnnts are rinsed thoroughly with cold and hot water, optjor>aHy with the addition of an agent that has a dispersing action and promotes the diffusion of unfixed dye
The dyes accordir^ to the invention are distinguished by high reactivity, good fixing ability £Mid a very good buiid-up behaviour. They can accordingly be used in accordance with the ffichaust dyeing method at low dyeing temperatures and require only short st^iming times in the pad-steam m^hod. The degrees of fixing are high and unfixed dye can be washed off easily, the difference between the degree of exhaust and the degree of fixing being remarkaWy small, that is to say the soaping loss being very low The dyes according to the invention are also suitable especially for printing, more especially on cotton, twt are equally suitable also for pnnttng nitrogen-containing fibres, for example wool or silk or blend fabrics that comprise wool or silk
The dyeings and prints produced using the dyes according to the invention have a high tinctorial strength and a high fil»re-to-dye binding stability in both the acidic and the alkaline range, and furthermore have good fastness to light and very good wet-fastness prof^rties, such as fastness to washing, to water, to sea water, to cross-dyeing and to perspiration, as
well as good fastness to pleating, to ironing and to rubbing The dyeings obtained exhibit fibre levelness and surface levelness
The dyes of formula (1) according to the invention are also suitable as colorants for use in recording systems. Suitable recording systems are, for example, commercially available ink-jet printers for paper or textile printing, or wnting instruments, such as fountain pens or ballpoint pens, and especially ink-jet printers For that purpose, the dyes accwding to the invention are first of ail brought into a form suitable for use in recording systems. A suitable form is, for exampte, an aqueous ink, which comprises the dyes according to tie invention as colorants. The inks can be prepared in customary manner by mixing together the individual components in the desired amount of water
As substrates there come into consideration the above-mentioned hydroxyl-group-containing or nitrogen-containir^ filwre materials, especially cellulosic fibre materials. The fibre materials are preferably textte fibre matenals
Substrates that also come into consideration are paper and plastics films
As examples of paper there may be mentioned commercially available ink-jet paper, photo paper, glc^sy paper, plastics-coated paper, e.g. Epson Ink-jet Paper, Epson PhcAo Paper, Epson Glossy Paper, Epson Glossy Film, HP Special Ink-jet Paper, Encad Photo Gloss Paper and llford Photo Paper. Plastics films are, for example, transparent or doudy/opaque. Suitable plastics films are, for example, 3M Transparency Film.
Depending on the nature of the use, for example textile printing or paper pnntirig, it may be necessary, for example, for the viscosity or other physical properties of the ink, especially properties that have an influence on the affinity for the substrate in question, to be adapted accordingly.
The dyes used in the aqueous inks should preferably have a low salt content, that is to say they shoutel have a total content of salts of less than 0.5 % by weight, based on the weight of the dyes. Dyes that have relatively high salt contents as a result of their preparation and/or as a result of the sukBequent addition of diluents can be desalted, for example by membrane separation procedures, such as ultrafiltration, reverse osmosis or dialysis
The inks preferably have a total content of dyes of from 1 to 35 % by weight, especially from 1 to 30 % by weight and preferably from 1 to 20 % by weight, based on the total weight of the ink. The preferred tower limit in this case is a limit of 1.5 % by weight, preferably 2 % by weight and especially 3 % by weight
The inks may compsise water-mlscible organic solvents, for example C1-C4alcohols, e g. nrwBthanol, ethanol, n-prqjanol, isopropanol, n-butanol, sec-butanol, tert-butanol or iso-butanol, amides, e.g. dimethytformamide or dimethylacetamide, ketones or kelone alcohols, e.g. acetone or diacetone ala)hol; ethers, e g. tetrahydrofuran or dioxane. nitrogen-containing heterocyclic ajmfwunds, e.g N-methyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidone, polyaU$ylene glycols, e.g. polyethylene glycol or polypropylene glycol, C2-C6alkylene glycols and ttwoglycols, e.g ethylene glycol, propylene glycol, butytene glycol, triethylene glycol, thtoctigiycol, hexylene glycol and diethylene glycol, other polyols, e.g gfycerol or 1,2,6-haxanetriol; and C1-C4alkyl ethers of polyhydric alcohols, e.g. 2-methoxy-etianol, 2-(2-meth0xyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxy-e^oxy)ethoxy]ethanoi or 2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyi-2-pyrrolidone, diethylene glycol, glycerol or especially 1,2-propylene glycol, usually in an amount of from 2 to ^ % by weight, especially from 5 to 30 % by weight and preferably from 10 to 25 % by weight, based on the total weight of the ink.
In addition, the inks may also comprise solubilisers, e.g. e-caprolactam
The inks may comprise thickeners of natural or synthetic origin, inter alia for the purpose of adjusting the viscosity.
Examples of thickenws that may be mentioned include commercially available alginate thickeners, starch ethers or tocust bean flour ethers, especially sodium alginate on its own or in admixture with modified cellutose, e.g methyl cellulose, ethyl cellulose, carljoxymethyi cellulose, hydroxyethyl cellutose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl meth^ cellulose, especially with preferably from 20 to 25 % by weight carboxymethyl celtolose. Synthetic thickeners that may be mentioned are, for example, those based on poly(metti)acrylic acids or poly(meth)acrylamides and also polyalkylene glycols having a molecular weigtit of, for example, from 2000 to 20 000, such as, for example.
polyethylene glycol or polypropylene glycol or mixed polyalkylene glycols of etl^lene oxide and propylene oxide.
The inks comprise such thickeners, for example, in an amount of from 0 01 to 2 % by weight, especially from 0.01 to 1 % by weight and preferably from 0 01 to 0 5 % by we^ht, based on the total weight of the ink
The inks may also comprise buffer substances, e.g. borax, borates, phosphates, poly-phosphates or citraies. Examples that may be mentioned include borax, sodium borate, sodium tefraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate and sodium citrate. They are used especially in amounts of from 0.1 to 3 % by weight, preferably from 0 1 to 1 % by weight, based on the total weight of the ink, in order to establish a pH value of, for example, from 4 to 9, especially from 5 to 8.5
As further additives, the inks may compnse surfactants or humectants
Suitable surfactants include commercially available anionic or non-ionic surfactants As humectants in the inks according to the invention there come into consideration, for example, wea or a mixture of sodium lactate (advantageously in the form of a 50 % to SO % aqueous solution) and glycerol and/or propylene glycol in amounts of preferably from 0.1 to 30 % by weight, especially from 2 to 30 % by weight
Preference is given to Inks having a viscosity of from 1 to 40 mPa s, especially from 1 to 20 mPas and more especially from 1 to 10 mPa s
Furthermore, the mks may in addition comprise customary additives, e.g. anti-foams or especially preservatives that inhibit fungal and/or bacterial growth Such additives are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the ink
As preswvatives there come into consideration formaldehyde-yielding agents, for example paraformaldehyde and trioxane, especially aqueous, approximately from 30 to 40 % by weight formaldehyde solutions, imidazole compounds, for example 2-(4-thiazolyl)-benzimidazole, thiazoie compounds, for example 1,2-benzisothiazolin-3-one or 2-n-octyl-
isothiazolin-3-one, iodine compounds, nitnles, phenols, haloalkylthio compounds or pyridine derivatives, especially 1,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-or*e A suitable preservative is, for example, a 20 % by weight solution of 1,2-benzisothiazolin-3-one in dipropylene glycol (Proxel® GXL).
The inks may also comprise further additives, such as fluorinated polymers or telomers, for example polyethoxyperfluoroalcohols (Forafac® or Zonyl® products) in an amount of, for example, from 0.01 to 1 % by weight, based on the total weight of the ink
In the case of the ink-jet pnnting method, individual droplets of ink are sprayed onto a substrate from a nozzle in a controlled manner. It is mainly the continuous ink-|et method and the droß-on-demand method that are used for that purpose. In the case of the continuous ink-jet method, the droplets are produced continuously, droplets not required for the printing operation being discharged into a receptacle and recycled. In the case of the drop-on-ctemand method, on the other hand, droplets are generated as desired and used for printing, that is to say, droplets are generated only when required for the pnnting operation The production of the droplets can be effected, for example, by means of a piezo ink-jet head or by thermal energy (bubble jet). Preference is given to printing by means of a piezo ink-jet head and to printing according to the continuous ink-jet method
The present inventfon accordingly relates also to aqueous inks that comprise the dyes of formula (1) according to the invention and to the use of such inks in an ink-jet pnnting method for printing a variety of substrates, especially textile fibre materials, the definitions and preferences indkated above applying to the dyes, the inks and the substrates.
The follovwng Examfi^s serve to illustrate the invention Unless otherwise indicated, the temperatures are pven in degrees Celsius, parts are parts by weight and percentages relate to % by weight. Parts by weight relate to parts by volume in a ratio of kilograms to litres
Example 1 •
(a) 40 parts of a neufral solution of 1-amino-8-hydroxynaphthalene-3,6-disulfc»iic acid (H-acid) in 200 parts of water are added drop wise at pH 2-2 5 and 0-5°C to a fine suspension of 23.5 parts of cyanuric chloride in 100 parts by volume of water and 100 parts of ice The mixture is adjusted to pH 2.5 by means of hydrochlonc acid. During the additicsi the reaction

temperature is maintained at 0-5°C by cooling After the addition is finished the pH is maintained at pH 2 with a soda ash solution (20%) until the reaction is complete
(b) A neutral soiution of 35 parts of 3-(ß-sulfatoethylsulfonyl)aniline in water is added to the reaction mixture oWaned according to (a) The pH is adjusted to 4.5-5 with a soda ash solution (20%) and maintained at these conditions. The temperature is nsing (5-25°C) until the reaction is complete The mixture obtained contains a compound which, in the form of the free acid, corresponds to formula
(Formula Removed)
(c) 31 parts of hydrochlonc acid (32%) are added to a neutral solution of 105 parts of the following intermediate
(Formula Removed)
in 4000 parts of water. 32 parts by volume of sodium nitrite 4 N are added drop wise at 20-30°C to this solution. An excess of sodium nitnte must be indicated by starch-iodide paper after the addition is finished. The reaction mass is stirred until diazotization is complete. Excess erf nitrite is then removed by addition of sulfamic acid
(d) The diazo mi)^ure obtained according to (c) is dosed to the cooled mixture obtained according to (b) at 5 to 25'C maintaining the reaction mixture at pH 6 5-7.5 by means of sodium hydroxide solution. The resulting reaction mass is stirred until couplir^ is complete, desalinated by dialysis and dried by lyophitisation A dye is obtained as a powder (max = 518 nm) which, in the form of the free acid, corresponds to formula

(Formula Removed)………………101
The dye prints or dyes cellulose in a briihant red shade with good fastness properties.
Examples 2 to 9: Analogously to the procedure described in Example 1, the compounds of
formulae
(Formula Removed)……………… 102 to 109
(max = 514 nm)
can be prepared, which likewise yield brilliant red shaded dyeings or prints on cellulose having good fastness properties.
Dyeing procedure I
X% (see Table 1 betow) of the dyestuff of formula (101) according to Example 1 or the dyestuff known in the art according to formula (110), respectively, are dissolved in 400 parts of water. To this solution are added 500 parts of a solution which contains Y gfl (see Table 1 below) of common salt (sodium chlonde). 100 paris of non-mercerized cotton tricot are introduced into the dye bath at 80°C. The temperature is maintained for 15 minutes and then increased to 90°C within 5 minutes. After 30 minutes at 90°C the temperature is decreased to 70°C within 10 minutes whereupon 100 parts of a solution containing Z1 g/l (see Table 1 below) of calcined sodium carbonate (soda ash) are added After 15 minutes at 70°C Z2 ml/1 (see Table 1 below) NaOH (36Be) are added. Dyeing is continued for a furth®r 30 minutes at this temperature. The dyed goods are then rinsed, soaped at the boil for a cfuarter of an hour with a non-ionic detergent, nnsed again and dried
(Formula Removed)………………110
Table 1: Salt and Alkali Recommendations
(Tabble Removed)
Tabte 2: Build-up : dependence of reference depth (RP) from dyestuff concentration
(Tabble Removed)
Table 2 shows that build-up of the dyestuff of formula (101) according to Example 1 is superior to the build-up properttes of the dyestuff of formula (110) known in the art. Furthermore, washing-off properties of the dyestuff of formula (101) according to the present invention are improved with respect to the dyestuff of formula (110).
Degree of fixation of the dyestuff of formula (101) according to the present invenntion is 75%, whereas the dyestuff of formula (110) known in the art shows a degree of fixation of only 66%.
Dyeing procedure ll
100 parts of cotton fabric are introduced at 70°C into 1500 parts of a dye bath containing 20 g/l of sodium chloride and 2 parts of the reactive dye obtained according to Example 1. After 45 minutes at 70°C, 5 g/l of calcined soda and after additional 10 minutes 2 ml/I NaOH (36°Be) are added. Dyeing is continued for a further 45 minutes at that temperature. The dyed goods are then rinsed, soaped at the boil for a quarter of an hour with a non-ionic detergent, rinsed again and dried
As an alternative to the above procedure, the dyeing can be carned out at 80°Cinstead of at 70°C
Dyeing procedure III
0.1 part of the dye according to Example 1 is dissolved in 200 parts of water, and 0.5 part of sodium sulfate, 0 1 part of a leveling agent (based on the condensation produet of a higher aliphatic amine and ethylene oxide) and also 0 5 part of sodium acetate are added. The pH is then adjusted to a value of 5.5 using acetic acid (80 %). The dye bath is heated at 50°C for 10 minutes and then 10 parts of a woollen fabnc are added Heating is then carried out in the course of approximately 50 minutes to a temperature of 100°C and dyeing is carried out at that temperature for 60 minutes, after which the dye bath is allowed to cool to 90°C and the dyed goods are removed. The woollen fabnc is washed with hot and cold water and is then spun and dried
Pnnting procedure I
3 parts of the dye obtained according to Example 1 are spnnkled, with rapid stirring, into
100 parts of a stock thickener containing 50 parts of 5 % sodium alginate thickener,
27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts
of sodium hydrogen carbonate The pnnt paste so obtained is used to print a cotton fabric,
and the resulting printed matenal is dried and steamed in saturated steam for 2 minutes at
102°C. The printed fabric is then nnsed, if desired soaped at the boil and rinsed again, and
subsequently dried.
Printing procedure II
(a) Mercensed cotton satin is pad-dyed with a liquor containing 30 g/1 of sodium carnonate and 50 g/1 of urea (70 % tiquor pick-up) and dried
(b) Using a droß-on-demarnd ink-jet head (bubble jet), the cotton satin pretreated according to Step (a) is printed with an aqueous ink containing

- 15 % by weight of the reactive dye of formula (101) according to Example 1,
- 15 % by weight of 1,2-propylene glycol and
- 70 % by weight of water
The print is dried compietety and fixed in saturated steam for 8 minutes at 102°C, cold-rinsed, washed off at the boil, rinsed again and dned.

We Claims :-
1. A reactive dye of formula
(Formula Removed)
wherein
R1 and R2 independently of one another are hydrogen or unsubstituted or substituted C1-
C4a!kyl,
D is a radical of a diazo component of the formula
(Formula Removed)
X1 and X2 independently of one another are halogen, T is a fibre-reactive radical of the formula
(Formula Removed)………..3a to 3g
(R3)0-2 denotes from 0 to 2 identical or different substituents from the group halogen,
C1-C4alkyl, C1-C4alkoxy and sulfo,
Z is vinyl or a -CH2-CH2-U radical and U is a group that is removable under alkaline
conditions,
Q is a -CH(Hal)-CH2-Hal or -C(Hal}=CH2 group,
Hal is halogen,
n is the number 0,1 or 2, and
m and q are independently of one another the number 0 or 1.
2. A reactive dye according to claim 1, wherein R1 and R2 are hydrogen.
3. A reactive dye according to either claim 1 or claim 2, wherein X1 and X2 indeperidently from one another are chloro or fluoro.
4. A reactive dye according to any one of claims 1 to 3, wherein Z is vinyl, ß-chloroethyl or ß-sulfatoethyi.
5. A reactive dye according to any one of claims 1 to 4 that corresponds to formula

(Formula Removed)
wherein
D, X1, X2, T and m are each as defined in claim 1.
6. A reactive dye according to claim 5, wherein
T is a radical of formula
(Formula Removed)
(R3)0-2 denotes from 0 to 2 identical or different substituents from the group nrpthyl, methoxy
and sulfo,
Z is vinyl, ß-chloroethyl or ß-sulfatoethyl,
Me is the methyl radical and Et the ethyl radical, and
m is the number 1.
7. A reactive dye according to either claim 5 or claim 6, wherein
D is a radical of a diazo component of the formula
(Formula Removed)
X1 and X2 are chlorine, T is a radical of formula
(Formula Removed)
Z is vinyl or ß-sulfatoethyl, m is the number 1, and q is the number 0.
8. A process for the preparation of a reactive dye of formula (1) according to daim 1, which comprises reacting with one another, in a suitable order, the compounds of formulae

(Formula Removed)……..4 to 10
wherein D, R1, R2, Xi, X2, T, n and m are each as defined in claim 1, by condensation, diazotation and coupling reactions.
9. The use of a readive dye according to any one of claims 1 to 7 or of a reactive dye prepared according to claim 8 in the dyeing or printing of hydroxyl-group-containing or nitrogen-containing fibre material.
10. Use according to claim 9, wherein cellulosic fibre material, especially cottpn-containing fibre material, is dyed or printed.
11. An aqueous ink that comprises a reactive dye of formula (1) according to claim 1.
12. A process for printing textile fibre material, paper or plastics film according to the ink-jet printing method, which comprises using an aqueous ink according to claim 11.

Documents:

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Patent Number

279893

Indian Patent Application Number

10301/DELNP/2008

PG Journal Number

05/2017

Publication Date

03-Feb-2017

Grant Date

01-Feb-2017

Date of Filing

12-Dec-2008

Name of Patentee

HUNTSMAN ADVANCED MATERIALS (SWITZERLAND) GMBH

Applicant Address

KLYBECKSTRASSE 200, 4057 BASEL, SWITZERLAND.

Inventors:

#	Inventor's Name	Inventor's Address
1	GEORG ROENTGEN	POCHGASSE 13, 79104 FREIBURG, GERMANY.
2	LASZLO FEKETE	UNTERE HOFMATTSTRASSE 39, 4312 MAGDEN, SWITZERLAND.

PCT International Classification Number

C09B 62/44

PCT International Application Number

PCT/EP07/057873

PCT International Filing date

2007-07-31

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	06118789.4	2006-08-11	EPO