Indian Patents. 211109:DISPERSE DYE MIXTURES

Title of Invention	DISPERSE DYE MIXTURES
Abstract	A dye mixture comprises (A) at least one monoazo dye of formula (I) wherein XA is C1, Br, I, CN or NO2; RA is C1-4alkyl or NHCOQ, where Q is C1-4alkyl; and each of RA¹ and RA², independently, is C1-4alkyl, C2-4alkenyl, C1-4alkoxy-C1-4alkyl, aryl-C1-4 alkyl or aryloxy-C1-4alkyl; and (B) at least one pyrroline type dye of formula (II) wherein Rв¹ is H, C1-20alkyl or C2-20alkenyl; and D is aryl.

Full Text	FORM 2 THE PATENTS ACT 1970 [39 OF 1970] COMPLETE SPECIFICATION [See Section 10]" "DISPERSE DYE MIXTURES" BASF AKTIENGESELLSCHAFT, a German company, of D-67056 Ludwigshafen, Germany, The following specification particularly describes the nature of the invention and the manner in which it is to be performed:- 5-11-2004 WO 00/32697 PCT/GB99/04026 DISPERSE DYE MIXTURES This invention relates to mixtures of disoerse dyes, compositions comprising dispersions of such mixtures and processes for the colouration of svntheti materials with such mixtures . More particularly, the invention relaces to mixtures of reddish blue monoazo dyes with those of the so called pyrroline type, which tend to be greenish blue. Monoazo dyes of the above type are disclosed in EP-A-0300626 and E9-A-0347685. As a component of a mixture of dyes, EP-A-0300626 discloses a dye of the formula where X is Br, C1 or I; Q is C,_.,alkyl; and each of Rl and R2 indeoendently is C 1-4 alky! or C2-4 alkeny1. Similarly, as a component of a mixture of dyes, EP-A-03476S5 discloses a dye of the formula WO 00/32697 PCT/GB99/04026 wherein Y is NO, or CN, R1 is alkyi, araikyl, alkoxyaikyi or alkenyl and R2 is alkyi, araikyl.. alkoxyaikyi, alkenyl, chloroalkyl, taryloxyalkyl or aikoxycarbonyalkyl Such dyes are in admixture with, for example, monoazo-dyes containing a tniophene nucleus . WO-A-97004030 discloses mixtures of the following dye with a thiophene dye in various proportions. 10 15 NHCOCH, 20 Dyes of disclosed, fc. G3-A-2I914 93, 94010243 . the abovementioned ovrroline tyoe are : example, in US-A-3G13Q13, US-A-3013013 EP-A-0327077, EP-A-G511S25 and WO-A- 25 In particular, WO-A-94010243 discloses dyes of the pyrroline type having- the formula (I) - 30 35 WO 00/32697 PCT/GB99/04026 wherein D is a group of the Formula (21 Formula (2) 10 or a group of Formula (3) •. Formula (3. or a group of the Formula (4) 20 A N 25 Rl and R2 RJ is aikyl, cycioalkyi, aryl, alkenyl or aralkyi each of which may be optionally substituted; is optionally substituted C7-2C.-alkyl; or together with the nitrogen atom to which they are attached form a pyrrolidine or piperidino ring,- is aikyl, alkenyl or aralkyi each of which may be optionally substituted, -SO1alkyl, -S02aryl, or -COR in which R is -H or aikyl, phenyl, cycioalkyi or aralkyi each of which may be optionally substituted or -H and WO 00/32697 PCT/G B99/04026 R" RS xs an electron wxtnGrawxng group,-is ODcicnally substituted C,. 10 15 20 aikyl; or R1 and R° together with the nitrogen atom to which they are attached form a pyrrolidine or pioeridino ring,- R7, R3, R" and R" each independently is aikyl, cycioaklyi, aryl, alkenyi or aralkyl, each of which may be optionally substituted, or -K; W is oxygen cr sulphur; Z is a direct link or N-R11 in which R11 is -H or optionally substituted alkyi or aryi; Ring A is unsubstituted apart from, the -NR/R2 group or is substituted by from 1 to 4 further groups,-and Ring 3 is unsubstituted or substituted by from 1 to 3 groups; except for 3-(4-(N-, N-di-n-octylamino)phenyl)-4-cyano-5-dicyano methylidene-2-oxo-2,5-dihydropyrrole provided that: (a) when D is a group of Formula \o;, " i "■ R1 and R" a: 25 ;H, wnen R3 different and R" is not -CI -CH,, phenyl, -CH.-phenvl and ethyl substituted by -On, ~CN, -OCHj, -OC,K,OCH5, - NHCO.CH, -Ophenyi and -MiSCUCEj; or (b) at least one of R1 and P.q is branched chain aikyl. Commercially available dyes of the pyrroiine type are, for example, dyes of the formula: 30 35 WO 00/32697 PCT/G 899/04026 liant 3lue F2B-5) ,-I-resn FG-3) ; and dye: where RA is H (Kayaion Polyester 3rii or CH;CH=CH, (Kayalon Polyester 31ue-C of the formula where XA is C4H9 and YA is CH (CH3) C5Hl2.. It is found that certain mixtures, although giving bright shades on polyester when viewed in normal daylight, tend to exhibit a "red" flare in tungsten light which is a serious commercial disadvantage. lease one of the mixtures disclosed in EP-A-G347535, such a mixture is especially sensitive to reduction and has a relatively low heat: fastness. Likewise flare can be avoided by using a dye mixture in which the nicrochioohene carries an acetyl group- However, such-dyes tend to be expensive. We have found surprisingly chat a mixture of dyes, as defined below, surprisingly not only allows reduction or even elimination of the "red" flare, but provides a much brighter shade and is less sensitive to reduction with consecruent loss of shade. Thus, the invention provides a mixture of dyestufis containing at least (A) at least one monoazo dye of the formula (I) WO 00/32697 PCT/GB99/0-4026 :D 10 wherein XA is Cl, Br, X, CM or NOZt- RA is C1-4alkyl (or NHCOQ, where Q is Chalky!) ; and each of RA* and RA2 independently is C1.4alkyl, C,_4alkenyi, C1-4alkoxy C1-4alkyl, aryl-C2-4 alky 1 or aryloxy-C1-4alkyl ; and (B) at least one dve of the formula (II) 15 20 25 30 wherein Ry is H, C1-20 alky or C2_20alkenyi; and D is aryi. In a preferred dye mixture, in a dye of the fannuls (I) of the mixture, an especially preferred value of XA is 3r or CN, especially preferred values of RA are NKCOCK NHCOC2K3r CH3 and C2H5 ana especially preferred values RA1 and RA2 are methyl, ethyl and allyi- 35 Typical especially preferred components (A) in mixtures embodying the invention are selected from (Al)a monoazo dye of the formula (I), wherein XA is Br, RA is NHCORx where Rx is methyl or ethyl and each of RAl and RAZ is ethyl; WO 00/32697 PCT/GB99/04026 (A2)a monoaza dye of the formula (I , wherein X4 i CN, RA is CH, and each of RAl and RA1 is ethyl; and (A3) a monoazo dye of the formula 11) , wherein XA is CN, R.A is CH3, RAL is methyl and RA2 is 3-phenylpropyl. The dyes of the formula {I) may be prepared in a conventional manner by diazotisation and coupling. 10 More particularly, for dyes wherein, in formula (I) XA is CI, Br or I, an amine of formula (III) 20 wherein X is C1, 3r, or I, is diazotised and copled with a couling component of the formula (V) (III) 25 (V) wherein RA, P^1 and RA2 are as defined abov; 30 35 Dyes of the formula (I) , wherein X; is CN may be prepared by diazotizing 2,6-dibromo-4-nitroaniline and coupling to a couoling component of the formula (V) to form a precursor dye and thereafter subjecting the precursor dye to a copper catalysed cya.no exchange reaction using, for example, copper cyanide or a mixture of copper and sodium cyanides, optionally in a solvent such as dimethyl formamide. WO 00/32697 PCT/GB99/04026 Similarly, dyes of the formula (I), wherein X, is MO, may be prepared by diazotizing 2-dibrcmc-4 , 5-dinitroaniline, coupling to a coupling componsnc of the formula (V) and then subjecting che resulting crecursor 5 dye to the above copper catalysed cyano exchange reaction.. In the above diazocisatian and" coupling reactions, the diazotizatian is carried out using a diazotising 10 agent, which is preferably nitrosyl sulphuric acid, optionally diluted with, glacial acetic acid or a phosphoric/acetic acid mixture and preferably at a temperature of 0-10°C, more preferably 0-5"C and preferably at a pH 15 0.5-1, followed by a subsequent increase in pH to 3-4 to isolate the dye. Reference is now made to component (3) , which comprises a pvrroline type dye of the formula (II)- In the compound of the formula II, D is prererabiy a group of the formula (a) . wherein each of R3Z and -32 independently is alkyl, cycloalkyl, aryl, aikenyl or aralkyi. 30 In the above formula (II), the alkyl group represented by any of R3-1-R 23 is preferably a C1-2-alkyl, more preferably a C1-12-alkyl and especially a C1-3-alkyl group. The cycloaikyl group represented by R.32 or R3 is 35 preferably a C4-8-cycloalkyl and more preferably a cyclohexyl group. The aryl group represented by R32 or 9 WO 00/32697 PCT/CB99/04026 R93 is preferably phenyl. The alkenyl group represented by any of R31-R33 is preferably a C2-14alkenyl, more preferably C2-5,-alkenyl and especially a C2_3-alkenyl group, such as allyl. The aralkyl group represented by any one of R2-1R35 is preferably a phenyl-C1-6-alkyi, more preferably a phenyl-C1-3-alkyl, especially phenyiethyl or 3-phenylpropyl. The alkyl group represented by R33 is more preferably a C7-15-alkyl, still more preferably a C-,.-.:-alkyl and especially a C7_9-alkyl group. The alkyl group represented by R3X is more preferably a C1-6-alkyl and still more preferably C1-4-alkyl group. Ra1 is especially preferably -H, C1-4alkyl or C2_3alkenyl, more preferably -H or CN..,-alkyl and especially -H. D is preferably a group of Formula (a) . The alkyl groups represented by any of R3"" - R23 may be straight or branched chain alkyl groups. R32 is preferably C1-12alkyl more preferably C3-3-alkyi especially unsubstituted C1-6 alky1 R33 may be C7-12alkyl and preferably C7_9-alkyl, especially unsubstituted C7.9-alkyl or may be unsubstituted Cw-alkyl. Where D is a group of Formula (a) it is preferred that one or botn of R.32 and R33 is branched, more preferably branched at an a- or P-, i.e., 1- or 2-, position. It is preferred that R32 and R.33 are different. It is also preferred that ring A is unsubstituted apart from the NR3ZR33 group. A preferred sub-group of dyes of Formula (I) is that in which D is a group of Formula (a): 10 WO 00/32697 PCT/GB99/040Z6 R81 is alkyl or -H; RB2 is alkyl; R33 C7_20-alkyl; and Ring A is unsubstituted apart from the NR32R33 grouo. 5 Another preferred sub-group of dyes of Formula (II) is that in which D is a group of the Formula (a) ; R31 is -H or alkyl; R32 is unsubstituted C1-3alkyl; 10 R33 is unsubstituted C1-5alkyl; Ring A is unsubstituted apart from the -NR32R93 group; and R32 and R33 are different or at least one of R32 and Ra3 is a branched chain alkyl. 15 An especially preferred sub-group cf dyes of Formula (II) is that in which D is a group of Formula (a) .-R31 is -H; R32 is unsubstituted C1-3aikyl,- R93 is unsubstituted C2-3alkyl; and 20 Ring A is unsuhstituced apart from the NR92R31 group . A further especially preferred sub-group of dyes of Formula (II) is that in which □ is a group of Formula (a) ; 25 R81 is -H; R32 is n-propyl or n-butyl; Ra3 is 1-methyihexyl or 2-ethylhexyi; and Ring A is unsubstituted apart from the -MR.32R93 group; 30 Typical especially preferred mixtures of components (B) in mixtures embodying the invention are selected from (Bl) a pyrroline type dye of the formula (II), wherein R3X is K, R32 is C4H, and R33 is 1-methyl-n-hexyl 35 (Bl) or a mixture thereof with up to 10%, by weight of 11 WO 00/3269" PCT/GB99/04026 component (31;, of a pyrroline type dye .32) of the formula (II), wherein Ra" is K and each of R32 and R3} is (B2) a pyrroline type dye of the formula (II), wherein Rg1 is H, R,2 is ethyl and R33 is n-octyl (33) , or 2-ethyl-n-hexyi (34) or a mixture of dyes- (3J) and .(3") ,-and (33) a pyrroline type dye of the formula (II), wherein R92 is C.H9, R93 is phenylpropyl and R81 is H (B3) or ally! (B°i or a mixture of dyes (3s) and (3s) . When R3 is H, dyes of Formula (II) may exist in a tautomeric form represented by Formula ,"IIA) -. Formula.(IIA) wherein D is as hereinbefore defined. The dyes cf Formula (II) where D is a group o-f Formula (a) may be prepared by reaction, of an aniline o£ Formula (III): Formula (III) in which Ring A is as hereinbefore defined, firstly with a compound of Formula R22X3 in which R32 is as hereinbefore WO 00/32697 PCT/G 899/04026 defined and X3 is a halogen such as -Ci, -3r or -I or other leaving group, such as a tosylste, mesylate or alkylsulphonate, in the presence of a base such as an alkali metal carbonate or alkaline earth metal carbonate such as K2CO3) or CaC03 and secondly with a comoound of formula, R33x in which R33 and X are as hereinbefore-defined in the presence of a base as above to farm an aromatic amine of Formula (IV); 10 Formula (IV) 15 Alternatively the aromatic amine of the Formula (IV) may be prepared by reductive alkylation of the aniline of 20 Formula (III) with an appropriate ketone or aldehyde. The reductive alkylation mav be performed m an inert liquid medium such as an alcohol or ester optionally in the presence of an acid such as an aliphatic carbcxylic acid, for example, acetic and propionic acids and 25 aromatic sulphcnic acid e.g. 4 - toluenesuiohonic acid using a metal or supported metal catalyst such as palladium or platinum on carbon and hydrogen, optionally at elevated temperature and pressure. Alternatively, reducing agents such as sodium borohydride may be used. 30 After the reductive alkylation a second alkyl group may be introduced as described above. The aromatic amine of Formula (IV) is then reacted with a 3-halopyrroie of Formula (V): 35 O 00/32697 PCT/GB99/040: >" 10 Formula (V) 15 in which RBl is as hereinbefore defined and X9 is preferably a halogen such as -C1 or Br co form a compound of Formula (II). The reaction may be performed in a liquid medium such as N,N-dimethylformamide, N,N-dimethy1acetamide, dimechyisuiphoxida,, suipholane, N- 20 methvlcyrrolidons, acetomtrila, toluene or cetrahydrcfuran or any mixture chereof and at a temperature from -20GC to 5 0°C. The product may be isolated by any convenient means such as pouring the reaction mixture into a mixture of ice and water and 25 recovering the precipitated product by filtration. The product may be purified by any convenient means such as trituration or recrystallisation from organic liquids particularly alkanols such as methanol, echanol and esters such as ethyiacetate or mixtures chereof. 30 The 3-halo-2-oxopyrrole of Formula (V) may be prepared by haiogenation of a compound which may be represented by Formulae (VI) , (VI1) and (VI2) 35 WO 00/32697 PCT/GB99/04"" formula (Vi) Formula (VI"-) formula (VI2) 10 15 20 25 with a haiogenating agent such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachioride, thionyl chloride or phosgene at a temperature of from -20°C to 5 0°C in a liquid medium such as N,N-dimechylformamide, N, N-diethylacetamide, dimethylsulphaxide, sulpholane, N-methylpyrrolidone, acetonitrile or tetrahydrofuran. The product may be used without isolation with improvement in yield in the preparation of compounds of Formula (II) described above or may be isolated by evaporating the liquid medium. Alternatively a compound of Formula {IV) may be reacted directly with the compound represented by Formulae (VI) , (VI1) or (VI2) in a liquid medium such as toluene in the presence of a haiogenating agent such as phosphorus oxychloride. The compounds represented by Formulae (VI) or (VI1) may be prepared by reaction of diethylcxaiate with a compound for Formula (VII); 30 35 Formula (VII) WO 00/32697 PCT/GB99/04026 in the presence of a base such as an alkali metal alkoxide preferably a sodium or potassium C1-5alkoxide and especially sodium or potassium methoxide, ethoxide, n- or iso-propoxide, n-, iso- or tertiary-butoxide in a liquid medium, preferably an alkanol such as methanol, ethanoi, n- or iso-propanoi or n-, iso- or tertiary-butanol, at a temperature- of from 10°C to 60°C. The product may be isolated by coaling the reaction mixture and collection by filtration. The compound of Formula (VII) may be prepared by ditnerization of malononitrile of Formula (VIII) -. NCCH2CN Formula (VIII) by reaction with a base such as sodium methoxide in a liquid medium such as methanol at a temperature of from -20°C to S0°C The product may be isolated by filtration. A dye on Formula (II) in which R3L is other than -K may be prepared by reaction of the corresponding dye of Formula (II) in which ?-=.L is -H in a liquid medium, preferably an ami.de such as dimethylformamide or an ether such as tetrahydrofuran or diethylether in the presence of a base, preferably an alkali metal carbonate such as potassium carbonate or an alkali metal hydride such as sodium hydride at a temperature of 0°C to 120°C with an appropriate alkylating or acylating agent. Where R3l is alky! an appropriate alkylating agent is an alkyl halide, preferably an alkyl iodide, bromide or chloride. Where R31 is alkenyl an appropriate alkylating agent is an alkenyl halide, preferably an alkenyl bromide. These dyes may be isolated by evaporating the liquid medium or by filtration from the reaction mixture. As previously mentioned, component (3) may be a mixture of two or more dyes of Formula (II) wherein S^1 to WO 00/32697 PCT/GB99/04026 R.33 inclusive, D and Ring A are as hereinbefore defined. In general, in a preferred mixture of components (A) and (3), the ratio, by weight, of component (A) : component (B) may be from 95:5 to 80:20 inclusive, for example from 85:15 to 35:65 inclusive, or from 70:30 to 40:60, depending upon the choice of dyestuff . In especially preferred mixtures of components (A) and (B), component (A) is selected from (Al) a monoazo dye of the formula (I), wherein XA is Br, RA is NHCOR* where Rx methyl or ethyl and each of RAX and RA2 is ethyl,- (A2) a monoazo dye of the formula (I), wherein XA is CN, RA is CH3 and each of RAl and RA2 is ethyl,- and (A3) a monoazo dye of the formula (I) , wherein XA is CN, RA is CH,, RA1 is methyl and RA2 is 3 -phenylpropyl; and component (B) is selected from (31) a pyrroline type dye of the formula (II), wherein R91 is H, R32 is C4H9 and R33 is 1-methyl-n-hexyl (B1) or a mixture thereof with up to 10%, "oy weight of component (Bl), of a pyrroline cype aye (32) , of formula (II), wherein, R31 is H, and each of R32 and R33 is C4H9 or (32) a pyrroline type dye of the formula (II), wherein R31 is H, R32 is ethyl and R,3 is n-octyl (B3) , or 2-ethyl-n-hexyl (34) or a mixture of dyes (B-3) and (3A) ; or (B3) a pyrroline type dye of the formula (II), wherein R32 is C4Hg, Ra3 is 3-phenylpropyl and Rg1 is H (BD) or allyl (3s) or a mixture of dyes (Bs) and (Bs) . Esoecially preferred compositions are the following two component mixtures: (1) Component (Al) 0 00/3269" PCT/G 899/04026 where R. is CH3 anc/ar C2il$. [the dye wherein R is ethyl is commercially available as CI. Disperse Blue 133]; and Component (Bl) CH(CH,)C,H.. [which dye tnav contain up co 10% by weight of the corresponding N, N-dibutyi compound] ,- (2) Component (A2) [available commercially as C.I. Disperse 3iue 3SS] ana Cotuoonent (Bl) WO 00/32697 PCT/CB99/04026 More especially preferred are mixture (1) of components (Al) and (31) in the ratio of 30:10 to 60:40 by weight, mixture (2) of components (Ai: and (31) in the ratio of 70:30 to 40.-50 by weight and mixture (3) of 5 components (A3) and (31) in the ratio of 70.-30 to 40: SO by weight. A mixture embodying the invention cf at least one dye of formula (I) (Component A) and at least one dye of the formula (II) (Component B) may additionally comprise 10 at least one other dye (Component C) , especially a yellow, orange, red or brown dye capable of producing a navy or black shade. Mixtures embodying the invention can be prepared by a number of methods including 15 (1) Co-crystallisation Typically, the dyes are dissolved in a hot solvent, for example, by placing the dyes in a suitable solvent 20 and heating uo to che reflux temperature of the solvent until the dves are dissolved, thereafter filtering to provide a solution, and then allowing the solution to cool and crystals to form. The resultant mixture may then undergo further processing, such as milling and 25 spray drying. Examples of suitable solvents for this process are organic, solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, amides, sulpnoxides, esters, ketones and ethers. Specific 30 examples of organic solvents are toluene, ethyl celiosolve, acetone, chlorobenzene, pyridine, dimethyl formamide, diraethylsulphoxide, ethyl acetate, benzene, tetrahydrofuran and cyclohexam. 35 WO 00/32697 PCT/C 899/0-4026 (2) Co-milline (a) The dyes are mixed and then milled together to give an intimate blend which is then spray dried to give 5 a solid mixture,or (b) each dye is milled separately and then mixed in the required ratio before spray drying. (3) Dry Blending 10 Each dye is spray dried separately and then mixed in the required ratio by a dry blending process. The mixtures give an especially bright shade without 15 exhibiting a red flare in tungsten light. The mixtures have high colour strength and can be readily and cost-effectively formulated. Mixtures embodying the invention provide especially 20 useful disperse dyes valuable for colouring synthetic textile materials and fiber blends thereof by exhaust dyeing, padding or printing, and may be formed into dispersions for this purpose. They may also be used in, for example, ink jet printing of textiles and non-25 textiles, dye diffusion, thermal transfer printing and in the colouration of plastics. According to other aspects, the invention provides a composition comprising at least the dye mixture and a 30 dispersing agent, surfactant or wetting agent, suitable for providing such a dispersion and also a process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material or fibre blend a mixture comprising at least one 35 dye of the formula (I) and at least one dye of the formula (II) . WO 00/32697 PCT/CB99/04026 The synthetic textile material may be selected from aromacic polyester, especially ooivethvlene terephthalate, polyavaide, especially pciyhexamethyiene adipamide, secondary cellulose acetate, cellulose triacetate, and natural textile materials, especially cellulosic materials and wool. An especiaily preferred textile material is an aromatic polyester or fibre blend thereof with fibres of any of the above mentioned textile materials. Especially preferred fibre blends include those of polyester-cellulose, such as polyester-cotton, and polyester-wool. The textile materials or blends thereof may be in the farm of filaments, loose fibres, yarn or woven or knitted fabrics. The mixtures of dyes of formulae (I) and (II) optionally in conjunction with other disperse dyes may be applied to the synthetic textile materials or fibre blends by processes which ars conventionally employed in applying disperse dyes to such materials and fibre blends. Suitable process conditions may be selected from the following (I) exhaust dyeing at a pH or from 4 to S.5, at a temperature of from I25°C to I40°C for from 10 to 12 0 minutes and under a pressure of from 1 to 2 bar, a sequestrant optionally being added,- (i"i) continuous dyeing at a pH of from 4 to o.S, at a temperature of from 190°C to 2253C for from 15 seconds to 5 minutes, a migration inhibitor optionally being added,- (iii) direct printing at a pH of from 4 to 6-5, at a temperature of from 1S0°C to 185°C for from 4 to 15 minutes for high temperature steaming, or at a temperature of from 190°C to 225°C for from 15 seconds to 5 minutes for ba! WO 00/32697 PCT/GB99/04026 heat or at a temperature of from 120°C to 140°C and 1 to 2 bar for from 10 to 45 minutes for pressure steaming, wetting agents and thickeners (such as alginates; of from 5 to 5 100% by weight of the dye optionally being added; (iv) discharge printing (by padding the dye an to the textile material, drying and overprinting) at a pK of from 4 to 6.5, migration inhibitors 10 and thickeners optionally being added; (v) carrier dyeing at a pH of from 4 to 6.5, at a temperature of from 95°C to 100"C using a carrier such as methylnaphthalane, diphenyiamine or 2-phenylphenoi, seguestrants 15 optionally being added; and (vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of S5GC fcr acetate or at a temperature of 9 0°C fcr triacetate and nylon 20 for from 15 to 30 minute"s, sequestrants optionally being added. In all the above processes, the dye mixture may be applied as a dispersion comprising from 0.001% to S, 25 preferably from 0.Q05 to 4%, of the dye mixture in an aqueous medium. A particular aspect of the invention provides a composition comnrising a mixture of dyes (I) and (II) , 30 optionally ac least one other disperse dye and, additionally, optionally at least one further ingredient conventionally used in colouring applications such as a dispersing agent, surfactant or wetting agent. The composition typically comprises from 1% to 65%, 35. preferably 10 to 60%, more preferably 20 to 55%, of the total dye mixture in a liquid, preferably an aqueous, or WO 00/32697 PCT/C 899/04026 solid medium. Liquid compositions are preferably adjusted to pH 2 to 7, more preferably PH 4 to 6. Typical examples of dispersing agent are lignosulphonates, naphthalene suiphonic acid/formaldehyde condensates and phenoi/cresoi/suiphaniiic acid/formaldehyde condensates, typical examples of wetting agent are aikyl aryl ethoxyiates which may be sulphcnated or phosphated and typical examples of other ingredients which may be present are inorganic salts, de-foamers such as mineral oil or nonanoi, organic liquids and buffers. Dispersing agents may be present at from 10% to 200% on the weight of the dye mixtures. Wetting agents may be used at from 0% to 2 0% on the weight of the dye mixtures. The compositions may be prepared by bead milling the dye mixture with glass beads or sand in an aqueous medium. The compositions may have further additions of dispersing agents, fillers and other surfactants and may be dried, by a technique such as spray drying, to give a solid composition comprising from 5% to 65% of dyestuff. In addition to the above-mentioned application processes, the dye mixtures mav be applied to synthetic textile materials and fibre blends by ink-jet printing, the substrates optionally having been pre-treated to aid printing. For ink-jet applications, the application medium may comprise water and a water-soluble organic solvent, preferably in a weight ratio of 1:93 to 99:1, more preferably 1.-95 to 50.-50 and especially in the range 10:90 to 40: SO. The water-soluble organic solvent preferably comprises a C,-C.-aikanol, especially methanol or ethanol, a ketone, especially acetone or methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone, a glycol, especially ethylene glycol, propylene glycol, WO 00/32697 PCT7GB99/04026 trimethylene glycol, butane-2 , 3 -diol, thicdiglycal or diethylene glycol, a glycol ether, especially ethylene glycol monomethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether, urea, a sulphone, especially bis-(2-hydroxyethyi! sulphone or mixtures thereof. 10 15 The dye mixtures may also be applied to textile materials using supercritical carbon dioxide, in which case the dye formulating agents may optionally be omitted. Embodiments of the present invention will now be described in more detail with reference to the following Examples, in which parts are by weight unless otherwise stated. Examples 1-2 Preparation for Individual Dves Example 1 20 25 NHCOCH. 30 35 2-bromo-4-nitro-6-cyanoaniline (24 pares) was stirred at 0-5°C with a mixture of acetic/propicnic acids (100 parts, 86:14). Nitrosyl sulphuric acid (35 parts, 40% solution in H2S04 was added gradually at 0-5°C and the mixture was stirred at that temperature for 60 ruins. The diazo solution was added to a coupling mixture of N,N-diethyl-m-aminoacetanilide (21.6 parts), water (100 parts), cone, sulphuric acid (20 parts) and sulphamic acid (7 parts), stirring at 0-5°C. WO 00/32697 PCT/G 899/04026 After stirring for a further 2 hours, the product was isolated by filtration, washed with cold water and dried at S0°C. Yield 3-9 parts. 5 g_xamola_2_ Preparation of 3- (4- (N-butvl-N- (l-methvlhexyl) amino) phenv1 - 4 - cya.no z 5 - dicvancmethvlidene - 2 -oxo - 2 . 5- dihvdrooyrro1e i) A mixture o£ aniline (100 parts), 2-heptanone (220 10 parts), 4-toluene sulpfronic acid (6 parts) and 3% palladium on carbon (5 parts) in a 1 litre autoclave was charged with, hydrogen to a pressure of 30 atmospheres and heated at 150°C for 40 hours. The cooled reaction mixture wa-s diluted with ethyl acetate, filtered, washed 15 with lN-hydrochloric acid (6 x 200 parts) and water (2 x 200 parts), the ethyl acetate was separated and dried (MgS04) before evaporating to leave N- (I-methylhexyl) aniline (76 parts, 37%). 20 ia) In an alternative procedure, N- (l-methvihexvi)aniline was oraoarsd as follows: To an ice cooled, stirred mixture of aniline (23 pares),-heptan-2-one (59 parts) and propionic acid (9 parts) was added sodium bare-hydride (9.8 parts) portionwise at such 25 a rate as to keep the temperature less than 53C. The reaction mixture was allowed to warm up to room temperature and stirred overnight. The reaction mixture was poured into an ice wacer mixture and extracted with ethyl acetate. The organic phase was washed with water, 30 2% hydrochloric acid and water. The dried organic phase was evaporated to leave N- (1-methylhexyl) aniline (53.5 parts, 93%) . 3 5 WO 00/32697 PCT/GB99/04026 ii) A mixture of N- (1-methyihaxyl) aniltne (75 parts), 1-bromobutane (55 parts) , anhydrous potassium carbonate (S3 parts) and DMF (150 parts"; was stirred while heating under reflux far 41 hours. An additional quantity of 1- 5 bromo butane (44 parts) was added and the mixture stirred while heating under reflux for a further 19 hours. The cooled mixture was poured into water (400 parts) a.nd the organic phase separated. The aqueous phase was extracted with toluene, the organic phases and toluene extract were 10 combined and washed with water (2 x 10 0 parts) before evaporating to leave N-butyl-N- (l-methylhexyl) aniline (72.8 parts, 44%) which was purified by vacuum distillation to give N-butyl-N- (1-methyihexyl) aniline b.pt 73-80°C, 2.5 mm Hg. 15 iia) In an alternative procedure, N-butyl-N-(1-methylhexyi) aniline was prepared as follows: A mixture of N-butylaniline (7.45 parts), anhydrous 20 potassium carbonate (7.5 parts), 2-brcmcheptane (13.5 parts) and DMF (25 pares) was stirred at 130°C for 35 hours. The reaccion mixture was poured into water, saturated with salt -and extracted with ethyl acetate. The organic phase was washed with water, dried (MgSOj 25 and evaporated to leave N-butyl-N- (l-methylhexyl) aniline (11.3 parts, approximately 50% strength). This material had acetic anhydride (10 parts) added to it prior to further use. 30 iii) A stirred mixture of the disodium salt of 4-cyano-5-dicyanomethylidene-3 -hydroxy-2 -oxo-2, 5 -cihydropyrrole (23 parts) and dry N, N-dimethylformamide (ISO parts) was cooled to -5°C to -10°C and N-n-butyl-N-(1-methylhexyi)aniline containing acetic anhydride (27%, 37 35 parts) was added followed by the dropwise addition of phosphorous oxychloride (25 parts) whilst maintaining,the WO 00/32697 PCT/GB 99/0402 6 temperature at lass than -5oC The mixture was allowed to warm to room temperature and stirred for 20 hours. The reaction mixture was poured into a stirred mixture of ice and water (400 parts) and acetone (400 parts) was 5 added before filtering off a solid. The solid was washed repeatedly with warm water (40°C) and then dried at 50°C to yield 3 - (4- (N-butyl-N- (1-methyihexyl) amino) phenyl) -4-cyano-5-dicyanomethylidene-2-oxo-2, 5-dihydrcpyrrole (26.8 parts, 65%) . A small sample of this material was 10 slurried in boiling methanol, collected by filtration, washed with methanol and dried at 50°C to give 3-(4-(N-n-butyl-N- (1-methylhexyl) amino)phenyl) -4-cyano-5-dicyanomethylidene-2-oxo-2, 5-dihydrapyrrole m-p.l8Q°C; Amax (CH2Cl:) S62nm (s max 60231) ; M/Z (HI) 415 (M\ 20%) , 15 400 (15), 372 (12), 344 (100), 283 (33) and 272 (25). Examples 3-4 Preparation of Mixtures Exams 1 -? 3 20 A mixture of 34.3 pares of Component (All , wherein Rx is methyl, and 5.75 pares of Component (Bl) is prepared by mixing the cwo dyes togecher and milling them as a 40% aqueous slurry with 20 pares of a high temperature stable dispersing agent until the dye 25 particle size (mean diameter) is in the range of 0.1 - 5 microns. This dispersion is standardised to a liquid brand containing 20.5% of the mixture, by the addition of S.5 30 parts of a humectant and water (to 100 parts). This liquid is especially suitable for use in the direct WO 00/32697 PCT/GB99/04026 printing and continuous dyeing of polyester and polyester/cellulose blends and can also be used for exhaust dyeing. 5 The same dispersion is standardised to a solid brand containing 41% of the mixture and 59% dispersing agent, by the addition of the 39-parts of a temperature stable dispersing agent and drying to either a grain or powder form in a spray dryer. This product is especially 10 suitable for the exhaust dyeing of polyester, polyester/cellulose and polyester/wool blends and can also be used for continuous dyeing and direct printing.- A dyebath for the exhaust dyeing of polyester in 15 piece form is prepared by adding 3 mis of an aqueous dispersion of the solid brand (Ig dye in 10 0 ml water at 40-50°C) to 55.8 ml of de-ionised water and 1.2 ml of buffer solution. To this dyebath is added a 5g piece of polyester and the whole is held for 45 minutes at 130°C 20 in a Warner Mathis Labomat high temperature dyeing machine. After rinsing with water and a reduction clearing treatment, the material is dyed a bright reddish blue shade which apoears almost identical when viewed under both normal daylight and tungsten light sources. 25 Example 4 A mixture of 19.7 parts of Component (A2) and 12.17 parts of Component (Bl) is prepared by mixing the two 30 dyes together and milling them as a 40% aqueous slurry with 2 0 parts of a high temperature stable dispersing agent until the dye particle size (mean diameter) is m the range 0.1-5 microns. 35 The dispersion is standardised to a solid brand containing 31.9% of the mixture and 63.1% dispersing WO 00/32697 PCT/G 899/04026 agent, by the addition of 4a.1 parts of a high temperature stable dispersion agent and drying to either a grain or powder form in a spray dryer. This product is especially suitable for the exhaust dyeing of polyester, polyester/cellulose and polyester/wool blends and can also be used for continuous dyeing and direct printing. A dyebath for the exhaust dyeing of polyester in piece form is prepared by adding 3 mis cf an aqueous dispersion of the solid brand (Ig dye in 100 ml water at 40-50°CJ to 55.3 ml of de-ionised water and 1.2 ml of buffer solution. To this dyebath is added a 5g piece of polyester and the whole is held for 45 minutes at 13 0°C in a Werner Mathis Labomat high temperature dyeing machine. After rinsing with water and a reduction clearing treatment, the material is dyed a bright reddish blue shade which appears almost identical when viewed under both rorm.ai daylight and tungsten light sources. WE CLAIM: 1. A dye mixture comprising (A) at least one monoazo dye of the formula (I) en wherein X4 is CI, Br, I, CN or N02; RA is C1-4 alkyl or NHCOQ, where Q is C i-4 alkyl; and each of RA1 and RA2, independently, is C i-4alkyl, C 2-4 alkenyl, C M4alkoxy-Ci-4alkyl, aryl-Ci-4; alkyl or aryloxy- Ci-4alkyl; and (B) at least one pyrroline type dye of the formula (II). (ID wherein RB1 is H, C 1.20 alkyl or C 2-20 alkenyl; and D is aryl. 2. A dye mixture as claimed in claim 1, wherein, in a dye of the formula (I) of the mixture, XA; is Br or CN, RA is NHCOCH3, NHCOC2H5 CH3 or C2H5 and each or RA1 and RA2, independently is methyl, ethyl or allyl. 3. A dye mixture as claimed the formula (II) of the mixtui wherein each of RB2 and R B3 independently is alkyl,. cycloalkyl, aryl, alkenyl or aralkyl. 4. A dye, mixture as claimed in claim 3, wherein D is a group of the formula (a), RB2 is as defined in claim 3 and RB3 is optionally substituted C 7-20 alkyl. 5. A dye mixture as claimed in claim 4, wherein R B1 is H, R B2 is H, R B2is C4H9 and RB2 is 1-methyl-n-hexyl. 6. A dye mixture as claimed in claim 5, wherein component (B) is a pyrroline type dye (B1) of the formula (II) wnerein:R B1 is H R B2 is C4H9 and RB3 is 1-methyl-n-hexyl or is a mixture of the pyrroline-type dye (B1) with a pyrroline-type dye (B2) of the formula (II), wherein RB1 is H, and each of R B2 and R B3 is C4Hg, which pyrroline type dye mixture contains up to 10%, by weight of the total weight of the pyrroline-type dye mixture, of the dye (B2). 7. A dye mixture as claimed in claim 4, wherein component (B) is a pyrroline-type dye (B3) or (B4), each of the formula (II), or is a mixture of the dyes (B3) and (B4) which dye (B 3) is a dye wherein R B1 is H, R B2 is ethyl and R B3 is n- octyl and which dye (B4) is a dye wherein R B1 is H, R B2 is ethyl and RB2 is 2-ethyl and RB3 is 2-ethyl-n-hexyl. 8. A dye mixture as claimed in claim 3, wherein D is a group of the formula (a), RB2 is as defined in claim 3 and RB3 is optionally substituted C1-6 alkyl. 9. A dye mixture as claimed in claim 7, wherein RB1 is H or alkyl, RB2 is 3 -phenyl-n-propyl and R B3 is C4H9. 10. A dye mixture as claimed in claim 1, wherein the ratio, by weight, of dye (I): dye (II) is from 95:5 to 30:70. 11. A dye mixture as claimed in claim 10, wherein the said ratio is from 85:15 to 35:65. 12. A dye mixture as claimed in claim 11, wherein the said ratio is from 70:30 to 40:60. 13. A dye mixture as claimed in claim 1, which comprises, as component (A), a monoazo dye (Al) of the formula (I) wherein XA is Br, RA is NHCOQ, where Q is CH3 or C2H5 or a mixture of monoazo dyes (Al1) and (Al2) each of the formula (I) wherein, in each dye, XA is Br, in dye (All) RA IS NHCOCH3 and in dye (AP) RA is NHCOC2H5; and, as component (B), at least a pyrroline type dye (Bl) of the formula (II), wherein RB1 is Hand D is a group of the formula 9 GH(CH3HCH2\|4CH3 and optionally additionally up to 10% inclusive by weight of the total component (B) of a pyrroline type dye (B2) of the formula (II), wherein RB1 is H and D is a group of the formula 14. A dye mixture as claimed in claim 13, wherein the weight ratio of component (A): component (B) is from 90:10 to 80:20. 15. A dye mixture as claimed in claim 1, which comprises, as component (A), a monoazo dye (A2) of the formula (I), wherein X is CN, RA is CH3, and each of RA1 and RA2 is ethyl and as component (B), at least a pyrroline type dye (Bl) of the formula (II), wherein RB1 is H and D is a group of the formula CH{CH3HCH2)4CH3 and optionally additionally up to 10% inclusive by weight of the total component (B) of a pyrroline type dye (B2) of the formula (II), wherein R R RB 2 is H and D is a group of the formula 16. A dye as claimed in claim 15, wherein the weight ratio of component (A): component (B) is from 70:30 to 55:45. 17. A dye mixture as claimed in claim 1, which comprises, as component (A), a monoazo dye (A3) of the formula (I), wherein XA is CN, RA is CH3, RA1 is CH3 and R RA2 is 3-phenyl-n-propyl and as component (B), at least a pyrroline type dye (Bl) of the formula (II), wherein RB1 is Hand D is a group of the formula and optionally additionally up to 10% inclusive by weight of the total component (B) of a pyrroline type dye (B2) of the formula (II), wherein RB1 is H and D is a group of the formula 18. A dye mixture as claimed in claim 13, wherein the weight ratio of component (A): component (B) is from 70:30 to 55:45. 19. A composition comprising a dye mixture as claimed in anyone of the preceding claims and at least one dispersing agent, surfactant or wetting agent. 20. A process for colouring a synthetic textile material or fibre blend thereof, which comprises applying thereto a dye mixture as claimed in anyone of claims 1 to 19. 21. A process for colouring a synthetic textile material or fiber blend thereof, which comprises applying thereto a composition as claimed in claim 21, dispersed in an aqueous medium. 22. A process as claimed in claim 21 or claim 22, wherein the synthetic textile material or fiber blend thereof is a polyester or polyester-cellulose or polyester-wool blend. Dated this December 4, 2000. (RANJANA MEHTA DUTT) OF REMFRY AND SAGAR ATTORNEY FOR THE APPLICANTS

Full Text

FORM 2
THE PATENTS ACT 1970
[39 OF 1970]
COMPLETE SPECIFICATION
[See Section 10]"
"DISPERSE DYE MIXTURES"
BASF AKTIENGESELLSCHAFT, a German company, of D-67056 Ludwigshafen, Germany,
The following specification particularly describes the nature of the invention and the manner in which it is to be performed:-
5-11-2004

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PCT/GB99/04026

DISPERSE DYE MIXTURES
This invention relates to mixtures of disoerse dyes, compositions comprising dispersions of such mixtures and processes for the colouration of svntheti materials with such mixtures . More particularly, the invention relaces to mixtures of reddish blue monoazo dyes with those of the so called pyrroline type, which tend to be greenish blue.
Monoazo dyes of the above type are disclosed in EP-A-0300626 and E9-A-0347685.
As a component of a mixture of dyes, EP-A-0300626 discloses a dye of the formula

where X is Br, C1 or I; Q is C,_.,alkyl; and each of Rl and R2 indeoendently is C 1-4 alky! or C2-4 alkeny1.
Similarly, as a component of a mixture of dyes, EP-A-03476S5 discloses a dye of the formula

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wherein Y is NO, or CN, R1 is alkyi, araikyl, alkoxyaikyi or alkenyl and R2 is alkyi, araikyl.. alkoxyaikyi, alkenyl, chloroalkyl, taryloxyalkyl or aikoxycarbonyalkyl Such dyes are in admixture with, for example, monoazo-dyes containing a tniophene nucleus .
WO-A-97004030 discloses mixtures of the following dye with a thiophene dye in various proportions.

10
15

NHCOCH,

20

Dyes of disclosed, fc. G3-A-2I914 93, 94010243 .

the abovementioned ovrroline tyoe are : example, in US-A-3G13Q13, US-A-3013013 EP-A-0327077, EP-A-G511S25 and WO-A-

25

In particular, WO-A-94010243 discloses dyes of the pyrroline type having- the formula (I) -

30

35

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wherein
D is a group of the Formula (21

Formula (2)

10
or a group of Formula (3) •.

Formula (3.

or a group of the Formula (4)

20

A N

25

Rl and R2
RJ

is aikyl, cycioalkyi, aryl, alkenyl or aralkyi each of which may be optionally substituted; is optionally substituted C7-2C.-alkyl; or together with the nitrogen atom to which they are attached form a pyrrolidine or piperidino ring,-
is aikyl, alkenyl or aralkyi each of which may be optionally substituted, -SO1alkyl, -S02aryl, or -COR in which R is -H or aikyl, phenyl, cycioalkyi or aralkyi each of which may be optionally substituted or -H and

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R" RS
xs an electron wxtnGrawxng group,-is ODcicnally substituted C,.
10
15
20

aikyl; or
R1 and R° together with the nitrogen atom to which they are attached form a pyrrolidine or pioeridino ring,-
R7, R3, R" and R" each independently is aikyl, cycioaklyi,
aryl, alkenyi or aralkyl, each of which may be optionally
substituted, or -K;
W is oxygen cr sulphur;
Z is a direct link or N-R11 in which R11 is -H or optionally substituted alkyi or aryi;
Ring A is unsubstituted apart from, the -NR/R2 group or is substituted by from 1 to 4 further groups,-and
Ring 3 is unsubstituted or substituted by from 1 to 3 groups; except for 3-(4-(N-, N-di-n-octylamino)phenyl)-4-cyano-5-dicyano methylidene-2-oxo-2,5-dihydropyrrole
provided that:
(a) when D is a group of Formula \o;,
" i "■ R1 and R" a:

25

;H, wnen R3
different and R" is not -CI
-CH,, phenyl, -CH.-phenvl and ethyl substituted by -On,
~CN, -OCHj, -OC,K,OCH5, - NHCO.CH, -Ophenyi and -MiSCUCEj;
or
(b) at least one of R1 and P.q is branched chain aikyl.
Commercially available dyes of the pyrroiine type are,
for example, dyes of the formula:

30
35

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liant 3lue F2B-5) ,-I-resn FG-3) ; and dye:
where RA is H (Kayaion Polyester 3rii or CH;CH=CH, (Kayalon Polyester 31ue-C of the formula

where XA is C4H9 and YA is CH (CH3) C5Hl2..
It is found that certain mixtures, although giving bright shades on polyester when viewed in normal daylight, tend to exhibit a "red" flare in tungsten light which is a serious commercial disadvantage.
lease one of the mixtures disclosed in EP-A-G347535, such a mixture is especially sensitive to reduction and has a relatively low heat: fastness. Likewise flare can be avoided by using a dye mixture in which the nicrochioohene carries an acetyl group- However, such-dyes tend to be expensive.
We have found surprisingly chat a mixture of dyes, as defined below, surprisingly not only allows reduction or even elimination of the "red" flare, but provides a much brighter shade and is less sensitive to reduction with consecruent loss of shade.
Thus, the invention provides a mixture of dyestufis containing at least (A) at least one monoazo dye of the formula (I)

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:D

10

wherein XA is Cl, Br, X, CM or NOZt-
RA is C1-4alkyl (or NHCOQ, where Q is Chalky!) ; and
each of RA* and RA2 independently is C1.4alkyl, C,_4alkenyi, C1-4alkoxy C1-4alkyl, aryl-C2-4 alky 1 or aryloxy-C1-4alkyl ; and (B) at least one dve of the formula (II)

15
20

25
30

wherein Ry is H, C1-20 alky or C2_20alkenyi; and D is aryi.
In a preferred dye mixture, in a dye of the fannuls (I) of the mixture, an especially preferred value of XA is 3r or CN, especially preferred values of RA are NKCOCK NHCOC2K3r CH3 and C2H5 ana especially preferred values RA1 and RA2 are methyl, ethyl and allyi-

35

Typical especially preferred components (A) in mixtures embodying the invention are selected from
(Al)a monoazo dye of the formula (I), wherein XA is Br, RA is NHCORx where Rx is methyl or ethyl and each of RAl and RAZ is ethyl;

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(A2)a monoaza dye of the formula (I , wherein X4 i CN, RA is CH, and each of RAl and RA1 is ethyl; and
(A3) a monoazo dye of the formula 11) , wherein XA is CN, R.A is CH3, RAL is methyl and RA2 is 3-phenylpropyl.
The dyes of the formula {I) may be prepared in a conventional manner by diazotisation and coupling.

10

More particularly, for dyes wherein, in formula (I) XA is CI, Br or I, an amine of formula (III)

20

wherein X is
C1, 3r, or I, is diazotised and copled with a couling
component of the formula (V)

(III)

25

(V)

wherein RA, P^1 and RA2 are as defined abov;

30
35

Dyes of the formula (I) , wherein X; is CN may be prepared by diazotizing 2,6-dibromo-4-nitroaniline and coupling to a couoling component of the formula (V) to form a precursor dye and thereafter subjecting the precursor dye to a copper catalysed cya.no exchange reaction using, for example, copper cyanide or a mixture of copper and sodium cyanides, optionally in a solvent such as dimethyl formamide.

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Similarly, dyes of the formula (I), wherein X, is MO, may be prepared by diazotizing 2-dibrcmc-4 , 5-dinitroaniline, coupling to a coupling componsnc of the formula (V) and then subjecting che resulting crecursor 5 dye to the above copper catalysed cyano exchange reaction..
In the above diazocisatian and" coupling reactions, the diazotizatian is carried out using a diazotising
10 agent, which is preferably nitrosyl sulphuric acid, optionally diluted with, glacial acetic acid or a phosphoric/acetic acid mixture and preferably at a temperature of 0-10°C, more preferably 0-5"C and preferably at a pH 15 0.5-1, followed by a subsequent increase in pH to 3-4 to isolate the dye.
Reference is now made to component (3) , which comprises a pvrroline type dye of the formula (II)-
In the compound of the formula II, D is prererabiy a group of the formula (a) .

wherein each of R3Z and -32 independently is alkyl, cycloalkyl, aryl, aikenyl or aralkyi.
30
In the above formula (II), the alkyl group
represented by any of R3-1-R 23 is preferably a C1-2-alkyl,
more preferably a C1-12-alkyl and especially a C1-3-alkyl
group. The cycloaikyl group represented by R.32 or R3 is
35 preferably a C4-8-cycloalkyl and more preferably a
cyclohexyl group. The aryl group represented by R32 or
9

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R93 is preferably phenyl. The alkenyl group represented by any of R31-R33 is preferably a C2-14alkenyl, more preferably C2-5,-alkenyl and especially a C2_3-alkenyl group, such as allyl. The aralkyl group represented by any one of R2-1R35 is preferably a phenyl-C1-6-alkyi, more preferably a phenyl-C1-3-alkyl, especially phenyiethyl or 3-phenylpropyl.
The alkyl group represented by R33 is more preferably a C7-15-alkyl, still more preferably a C-,.-.:-alkyl and especially a C7_9-alkyl group.
The alkyl group represented by R3X is more preferably a C1-6-alkyl and still more preferably C1-4-alkyl group.
Ra1 is especially preferably -H, C1-4alkyl or C2_3alkenyl, more preferably -H or CN..,-alkyl and especially -H.
D is preferably a group of Formula (a) .
The alkyl groups represented by any of R3"" - R23 may be straight or branched chain alkyl groups. R32 is preferably C1-12alkyl more preferably C3-3-alkyi especially unsubstituted C1-6 alky1 R33 may be C7-12alkyl and preferably C7_9-alkyl, especially unsubstituted C7.9-alkyl or may be unsubstituted Cw-alkyl. Where D is a group of Formula (a) it is preferred that one or botn of R.32 and R33 is branched, more preferably branched at an a- or P-, i.e., 1- or 2-, position. It is preferred that R32 and R.33 are different. It is also preferred that ring A is unsubstituted apart from the NR3ZR33 group.
A preferred sub-group of dyes of Formula (I) is that in which D is a group of Formula (a):
10

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PCT/GB99/040Z6

R81 is alkyl or -H;
RB2 is alkyl;
R33 C7_20-alkyl; and
Ring A is unsubstituted apart from the NR32R33 grouo. 5
Another preferred sub-group of dyes of Formula (II) is that in which D is a group of the Formula (a) ;
R31 is -H or alkyl;
R32 is unsubstituted C1-3alkyl;
10 R33 is unsubstituted C1-5alkyl;
Ring A is unsubstituted apart from the -NR32R93 group; and R32 and R33 are different or at least one of R32 and Ra3 is a branched chain alkyl.
15 An especially preferred sub-group cf dyes of Formula
(II) is that in which D is a group of Formula (a) .-R31 is -H;
R32 is unsubstituted C1-3aikyl,-
R93 is unsubstituted C2-3alkyl; and
20 Ring A is unsuhstituced apart from the NR92R31 group .
A further especially preferred sub-group of dyes of
Formula (II) is that in which □ is a group of Formula
(a) ;
25 R81 is -H;
R32 is n-propyl or n-butyl; Ra3 is 1-methyihexyl or 2-ethylhexyi; and Ring A is unsubstituted apart from the -MR.32R93 group; 30
Typical especially preferred mixtures of components (B) in mixtures embodying the invention are selected from
(Bl) a pyrroline type dye of the formula (II), wherein R3X is K, R32 is C4H, and R33 is 1-methyl-n-hexyl 35 (Bl) or a mixture thereof with up to 10%, by weight of
11

WO 00/3269" PCT/GB99/04026
component (31;, of a pyrroline type dye .32) of the formula (II), wherein Ra" is K and each of R32 and R3} is
(B2) a pyrroline type dye of the formula (II), wherein Rg1 is H, R,2 is ethyl and R33 is n-octyl (33) , or 2-ethyl-n-hexyi (34) or a mixture of dyes- (3J) and .(3") ,-and
(33) a pyrroline type dye of the formula (II), wherein R92 is C.H9, R93 is phenylpropyl and R81 is H (B3) or ally! (B°i or a mixture of dyes (3s) and (3s) .
When R3 is H, dyes of Formula (II) may exist in a tautomeric form represented by Formula ,"IIA) -.

Formula.(IIA)
wherein D is as hereinbefore defined.
The dyes cf Formula (II) where D is a group o-f Formula (a) may be prepared by reaction, of an aniline o£ Formula (III):

Formula (III)
in which Ring A is as hereinbefore defined, firstly with a compound of Formula R22X3 in which R32 is as hereinbefore

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defined and X3 is a halogen such as -Ci, -3r or -I or other leaving group, such as a tosylste, mesylate or alkylsulphonate, in the presence of a base such as an alkali metal carbonate or alkaline earth metal carbonate such as K2CO3) or CaC03 and secondly with a comoound of formula, R33x in which R33 and X are as hereinbefore-defined in the presence of a base as above to farm an aromatic amine of Formula (IV);
10

Formula (IV)
15
Alternatively the aromatic amine of the Formula (IV) may be prepared by reductive alkylation of the aniline of
20 Formula (III) with an appropriate ketone or aldehyde.
The reductive alkylation mav be performed m an inert liquid medium such as an alcohol or ester optionally in the presence of an acid such as an aliphatic carbcxylic acid, for example, acetic and propionic acids and
25 aromatic sulphcnic acid e.g. 4 - toluenesuiohonic acid
using a metal or supported metal catalyst such as palladium or platinum on carbon and hydrogen, optionally at elevated temperature and pressure. Alternatively, reducing agents such as sodium borohydride may be used.
30 After the reductive alkylation a second alkyl group may
be introduced as described above.
The aromatic amine of Formula (IV) is then reacted with a 3-halopyrroie of Formula (V): 35

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PCT/GB99/040:

>*"

10
Formula (V)
15 in which RBl is as hereinbefore defined and X9 is
preferably a halogen such as -C1 or Br co form a compound of Formula (II). The reaction may be performed in a liquid medium such as N,N-dimethylformamide, N,N-dimethy1acetamide, dimechyisuiphoxida,, suipholane, N-
20 methvlcyrrolidons, acetomtrila, toluene or
cetrahydrcfuran or any mixture chereof and at a temperature from -20GC to 5 0°C. The product may be isolated by any convenient means such as pouring the reaction mixture into a mixture of ice and water and
25 recovering the precipitated product by filtration. The product may be purified by any convenient means such as trituration or recrystallisation from organic liquids particularly alkanols such as methanol, echanol and esters such as ethyiacetate or mixtures chereof.
30
The 3-halo-2-oxopyrrole of Formula (V) may be prepared by haiogenation of a compound which may be represented by Formulae (VI) , (VI1) and (VI2)
35

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formula (Vi)

Formula (VI"-)

formula (VI2)

10
15
20
25

with a haiogenating agent such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachioride, thionyl chloride or phosgene at a temperature of from -20°C to 5 0°C in a liquid medium such as N,N-dimechylformamide, N, N-diethylacetamide, dimethylsulphaxide, sulpholane, N-methylpyrrolidone, acetonitrile or tetrahydrofuran. The product may be used without isolation with improvement in yield in the preparation of compounds of Formula (II) described above or may be isolated by evaporating the liquid medium.
Alternatively a compound of Formula {IV) may be reacted directly with the compound represented by Formulae (VI) , (VI1) or (VI2) in a liquid medium such as toluene in the presence of a haiogenating agent such as phosphorus oxychloride.
The compounds represented by Formulae (VI) or (VI1) may be prepared by reaction of diethylcxaiate with a compound for Formula (VII);

30

35

Formula (VII)

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in the presence of a base such as an alkali metal alkoxide preferably a sodium or potassium C1-5alkoxide and especially sodium or potassium methoxide, ethoxide, n- or iso-propoxide, n-, iso- or tertiary-butoxide in a liquid medium, preferably an alkanol such as methanol, ethanoi, n- or iso-propanoi or n-, iso- or tertiary-butanol, at a temperature- of from 10°C to 60°C. The product may be isolated by coaling the reaction mixture and collection by filtration.
The compound of Formula (VII) may be prepared by ditnerization of malononitrile of Formula (VIII) -.
NCCH2CN
Formula (VIII)
by reaction with a base such as sodium methoxide in a liquid medium such as methanol at a temperature of from -20°C to S0°C The product may be isolated by filtration.
A dye on Formula (II) in which R3L is other than -K may be prepared by reaction of the corresponding dye of Formula (II) in which ?-=.L is -H in a liquid medium, preferably an ami.de such as dimethylformamide or an ether such as tetrahydrofuran or diethylether in the presence of a base, preferably an alkali metal carbonate such as potassium carbonate or an alkali metal hydride such as sodium hydride at a temperature of 0°C to 120°C with an appropriate alkylating or acylating agent. Where R3l is alky! an appropriate alkylating agent is an alkyl halide, preferably an alkyl iodide, bromide or chloride. Where R31 is alkenyl an appropriate alkylating agent is an alkenyl halide, preferably an alkenyl bromide. These dyes may be isolated by evaporating the liquid medium or by filtration from the reaction mixture.
As previously mentioned, component (3) may be a mixture of two or more dyes of Formula (II) wherein S^1 to

WO 00/32697

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R.33 inclusive, D and Ring A are as hereinbefore defined.
In general, in a preferred mixture of components (A) and (3), the ratio, by weight, of component (A) : component (B) may be from 95:5 to 80:20 inclusive, for example from 85:15 to 35:65 inclusive, or from 70:30 to 40:60, depending upon the choice of dyestuff .
In especially preferred mixtures of components (A) and (B), component (A) is selected from
(Al) a monoazo dye of the formula (I), wherein XA is Br, RA is NHCOR* where Rx methyl or ethyl and each of RAX and RA2 is ethyl,-
(A2) a monoazo dye of the formula (I), wherein XA is CN, RA is CH3 and each of RAl and RA2 is ethyl,- and
(A3) a monoazo dye of the formula (I) , wherein XA is CN, RA is CH,, RA1 is methyl and RA2 is 3 -phenylpropyl; and
component (B) is selected from
(31) a pyrroline type dye of the formula (II),
wherein R91 is H, R32 is C4H9 and R33 is 1-methyl-n-hexyl
(B1) or a mixture thereof with up to 10%, "oy weight of component (Bl), of a pyrroline cype aye (32) , of formula (II), wherein, R31 is H, and each of R32 and R33 is C4H9 or
(32) a pyrroline type dye of the formula (II),
wherein R31 is H, R32 is ethyl and R,3 is n-octyl (B3) , or
2-ethyl-n-hexyl (34) or a mixture of dyes (B-3) and (3A) ;
or
(B3) a pyrroline type dye of the formula (II), wherein R32 is C4Hg, Ra3 is 3-phenylpropyl and Rg1 is H (BD) or allyl (3s) or a mixture of dyes (Bs) and (Bs) .
Esoecially preferred compositions are the following two component mixtures:
(1) Component (Al)

0 00/3269"

PCT/G 899/04026

where R. is CH3 anc/ar C2il$.
[the dye wherein R is ethyl is commercially available as
CI. Disperse Blue 133]; and
Component (Bl)

CH(CH,)C,H..

[which dye tnav contain up co 10% by weight of the corresponding N, N-dibutyi compound] ,-
(2) Component (A2)

[available commercially as C.I. Disperse 3iue 3SS] ana Cotuoonent (Bl)

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More especially preferred are mixture (1) of
components (Al) and (31) in the ratio of 30:10 to 60:40
by weight, mixture (2) of components (Ai: and (31) in the
ratio of 70:30 to 40.-50 by weight and mixture (3) of
5 components (A3) and (31) in the ratio of 70.-30 to 40: SO
by weight.
A mixture embodying the invention cf at least one
dye of formula (I) (Component A) and at least one dye of
the formula (II) (Component B) may additionally comprise
10 at least one other dye (Component C) , especially a
yellow, orange, red or brown dye capable of producing a navy or black shade.
Mixtures embodying the invention can be prepared by a number of methods including 15
(1) Co-crystallisation
Typically, the dyes are dissolved in a hot solvent, for example, by placing the dyes in a suitable solvent
20 and heating uo to che reflux temperature of the solvent
until the dves are dissolved, thereafter filtering to provide a solution, and then allowing the solution to cool and crystals to form. The resultant mixture may then undergo further processing, such as milling and
25 spray drying. Examples of suitable solvents for this
process are organic, solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, amides, sulpnoxides, esters, ketones and ethers. Specific
30 examples of organic solvents are toluene, ethyl
celiosolve, acetone, chlorobenzene, pyridine, dimethyl formamide, diraethylsulphoxide, ethyl acetate, benzene, tetrahydrofuran and cyclohexam.
35

WO 00/32697 PCT/C 899/0-4026
(2) Co-milline
(a) The dyes are mixed and then milled together to
give an intimate blend which is then spray dried to give
5 a solid mixture,or
(b) each dye is milled separately and then mixed
in the required ratio before spray drying.
(3) Dry Blending
10
Each dye is spray dried separately and then mixed in the required ratio by a dry blending process.
The mixtures give an especially bright shade without 15 exhibiting a red flare in tungsten light. The mixtures have high colour strength and can be readily and cost-effectively formulated.
Mixtures embodying the invention provide especially 20 useful disperse dyes valuable for colouring synthetic textile materials and fiber blends thereof by exhaust dyeing, padding or printing, and may be formed into dispersions for this purpose. They may also be used in, for example, ink jet printing of textiles and non-25 textiles, dye diffusion, thermal transfer printing and in the colouration of plastics.
According to other aspects, the invention provides a composition comprising at least the dye mixture and a
30 dispersing agent, surfactant or wetting agent, suitable for providing such a dispersion and also a process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material or fibre blend a mixture comprising at least one
35 dye of the formula (I) and at least one dye of the formula (II) .

WO 00/32697 PCT/CB99/04026

The synthetic textile material may be selected from aromacic polyester, especially ooivethvlene terephthalate, polyavaide, especially pciyhexamethyiene adipamide, secondary cellulose acetate, cellulose triacetate, and natural textile materials, especially cellulosic materials and wool. An especiaily preferred textile material is an aromatic polyester or fibre blend thereof with fibres of any of the above mentioned textile materials. Especially preferred fibre blends include those of polyester-cellulose, such as polyester-cotton, and polyester-wool. The textile materials or blends thereof may be in the farm of filaments, loose fibres, yarn or woven or knitted fabrics.
The mixtures of dyes of formulae (I) and (II) optionally in conjunction with other disperse dyes may be applied to the synthetic textile materials or fibre blends by processes which ars conventionally employed in applying disperse dyes to such materials and fibre blends.
Suitable process conditions may be selected from the
following
(I) exhaust dyeing at a pH or from 4 to S.5, at a temperature of from I25°C to I40°C for from 10 to 12 0 minutes and under a pressure of from 1 to 2 bar, a sequestrant optionally being added,-
(i"i) continuous dyeing at a pH of from 4 to o.S, at a temperature of from 190°C to 2253C for from 15 seconds to 5 minutes, a migration inhibitor optionally being added,-
(iii) direct printing at a pH of from 4 to 6-5, at a temperature of from 1S0°C to 185°C for from 4 to 15 minutes for high temperature steaming, or at a temperature of from 190°C to 225°C for from 15 seconds to 5 minutes for ba!

WO 00/32697

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heat or at a temperature of from 120°C to 140°C
and 1 to 2 bar for from 10 to 45 minutes for
pressure steaming, wetting agents and
thickeners (such as alginates; of from 5 to
5 100% by weight of the dye optionally being
added; (iv) discharge printing (by padding the dye an to the textile material, drying and overprinting) at a pK of from 4 to 6.5, migration inhibitors
10 and thickeners optionally being added;
(v) carrier dyeing at a pH of from 4 to 6.5, at a temperature of from 95°C to 100"C using a carrier such as methylnaphthalane, diphenyiamine or 2-phenylphenoi, seguestrants
15 optionally being added; and
(vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of S5GC fcr acetate or at a temperature of 9 0°C fcr triacetate and nylon
20 for from 15 to 30 minute"s, sequestrants
optionally being added.
In all the above processes, the dye mixture may be applied as a dispersion comprising from 0.001% to S, 25 preferably from 0.Q05 to 4%, of the dye mixture in an aqueous medium.
A particular aspect of the invention provides a composition comnrising a mixture of dyes (I) and (II) ,
30 optionally ac least one other disperse dye and,
additionally, optionally at least one further ingredient conventionally used in colouring applications such as a dispersing agent, surfactant or wetting agent. The composition typically comprises from 1% to 65%,
35. preferably 10 to 60%, more preferably 20 to 55%, of the total dye mixture in a liquid, preferably an aqueous, or

WO 00/32697

PCT/C 899/04026

solid medium. Liquid compositions are preferably adjusted to pH 2 to 7, more preferably PH 4 to 6.
Typical examples of dispersing agent are lignosulphonates, naphthalene suiphonic acid/formaldehyde condensates and phenoi/cresoi/suiphaniiic acid/formaldehyde condensates, typical examples of wetting agent are aikyl aryl ethoxyiates which may be sulphcnated or phosphated and typical examples of other ingredients which may be present are inorganic salts, de-foamers such as mineral oil or nonanoi, organic liquids and buffers. Dispersing agents may be present at from 10% to 200% on the weight of the dye mixtures. Wetting agents may be used at from 0% to 2 0% on the weight of the dye mixtures.
The compositions may be prepared by bead milling the dye mixture with glass beads or sand in an aqueous medium. The compositions may have further additions of dispersing agents, fillers and other surfactants and may be dried, by a technique such as spray drying, to give a solid composition comprising from 5% to 65% of dyestuff.
In addition to the above-mentioned application processes, the dye mixtures mav be applied to synthetic textile materials and fibre blends by ink-jet printing, the substrates optionally having been pre-treated to aid printing. For ink-jet applications, the application medium may comprise water and a water-soluble organic solvent, preferably in a weight ratio of 1:93 to 99:1, more preferably 1.-95 to 50.-50 and especially in the range 10:90 to 40: SO. The water-soluble organic solvent preferably comprises a C,-C.-aikanol, especially methanol or ethanol, a ketone, especially acetone or methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone, a glycol, especially ethylene glycol, propylene glycol,

WO 00/32697

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trimethylene glycol, butane-2 , 3 -diol, thicdiglycal or diethylene glycol, a glycol ether, especially ethylene glycol monomethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether, urea, a sulphone, especially bis-(2-hydroxyethyi! sulphone or mixtures thereof.

10
15

The dye mixtures may also be applied to textile materials using supercritical carbon dioxide, in which case the dye formulating agents may optionally be omitted.
Embodiments of the present invention will now be described in more detail with reference to the following Examples, in which parts are by weight unless otherwise stated.

Examples 1-2 Preparation for Individual Dves Example 1

20
25

NHCOCH.

30
35

2-bromo-4-nitro-6-cyanoaniline (24 pares) was stirred at 0-5°C with a mixture of acetic/propicnic acids (100 parts, 86:14). Nitrosyl sulphuric acid (35 parts, 40% solution in H2S04 was added gradually at 0-5°C and the mixture was stirred at that temperature for 60 ruins. The diazo solution was added to a coupling mixture of N,N-diethyl-m-aminoacetanilide (21.6 parts), water (100 parts), cone, sulphuric acid (20 parts) and sulphamic acid (7 parts), stirring at 0-5°C.

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After stirring for a further 2 hours, the product was isolated by filtration, washed with cold water and dried at S0°C. Yield 3-9 parts.
5 g_xamola_2_
Preparation of 3- (4- (N-butvl-N- (l-methvlhexyl) amino) phenv1 - 4 - cya.no z 5 - dicvancmethvlidene - 2 -oxo - 2 . 5- dihvdrooyrro1e
i) A mixture o£ aniline (100 parts), 2-heptanone (220 10 parts), 4-toluene sulpfronic acid (6 parts) and 3%
palladium on carbon (5 parts) in a 1 litre autoclave was charged with, hydrogen to a pressure of 30 atmospheres and heated at 150°C for 40 hours. The cooled reaction mixture wa-s diluted with ethyl acetate, filtered, washed 15 with lN-hydrochloric acid (6 x 200 parts) and water (2 x 200 parts), the ethyl acetate was separated and dried (MgS04) before evaporating to leave N- (I-methylhexyl) aniline (76 parts, 37%).
20 ia) In an alternative procedure,
N- (l-methvihexvi)aniline was oraoarsd as follows: To an ice cooled, stirred mixture of aniline (23 pares),-heptan-2-one (59 parts) and propionic acid (9 parts) was added sodium bare-hydride (9.8 parts) portionwise at such
25 a rate as to keep the temperature less than 53C. The reaction mixture was allowed to warm up to room temperature and stirred overnight. The reaction mixture was poured into an ice wacer mixture and extracted with ethyl acetate. The organic phase was washed with water,
30 2% hydrochloric acid and water. The dried organic phase was evaporated to leave N- (1-methylhexyl) aniline (53.5 parts, 93%) .

3 5

WO 00/32697

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ii) A mixture of N- (1-methyihaxyl) aniltne (75 parts),
1-bromobutane (55 parts) , anhydrous potassium carbonate
(S3 parts) and DMF (150 parts"; was stirred while heating
under reflux far 41 hours. An additional quantity of 1-
5 bromo butane (44 parts) was added and the mixture stirred
while heating under reflux for a further 19 hours. The cooled mixture was poured into water (400 parts) a.nd the organic phase separated. The aqueous phase was extracted with toluene, the organic phases and toluene extract were
10 combined and washed with water (2 x 10 0 parts) before
evaporating to leave N-butyl-N- (l-methylhexyl) aniline (72.8 parts, 44%) which was purified by vacuum distillation to give N-butyl-N- (1-methyihexyl) aniline b.pt 73-80°C, 2.5 mm Hg.
15
iia) In an alternative procedure, N-butyl-N-(1-methylhexyi) aniline was prepared as follows:
A mixture of N-butylaniline (7.45 parts), anhydrous 20 potassium carbonate (7.5 parts), 2-brcmcheptane (13.5 parts) and DMF (25 pares) was stirred at 130°C for 35 hours. The reaccion mixture was poured into water, saturated with salt -and extracted with ethyl acetate. The organic phase was washed with water, dried (MgSOj 25 and evaporated to leave N-butyl-N- (l-methylhexyl) aniline (11.3 parts, approximately 50% strength). This material had acetic anhydride (10 parts) added to it prior to further use.
30 iii) A stirred mixture of the disodium salt of 4-cyano-5-dicyanomethylidene-3 -hydroxy-2 -oxo-2, 5 -cihydropyrrole (23 parts) and dry N, N-dimethylformamide (ISO parts) was cooled to -5°C to -10°C and N-n-butyl-N-(1-methylhexyi)aniline containing acetic anhydride (27%, 37
35 parts) was added followed by the dropwise addition of
phosphorous oxychloride (25 parts) whilst maintaining,the

WO 00/32697

PCT/GB 99/0402 6

temperature at lass than -5oC The mixture was allowed to warm to room temperature and stirred for 20 hours. The reaction mixture was poured into a stirred mixture of ice and water (400 parts) and acetone (400 parts) was 5 added before filtering off a solid. The solid was washed repeatedly with warm water (40°C) and then dried at 50°C to yield 3 - (4- (N-butyl-N- (1-methyihexyl) amino) phenyl) -4-cyano-5-dicyanomethylidene-2-oxo-2, 5-dihydrcpyrrole (26.8 parts, 65%) . A small sample of this material was
10 slurried in boiling methanol, collected by filtration,
washed with methanol and dried at 50°C to give 3-(4-(N-n-butyl-N- (1-methylhexyl) amino)phenyl) -4-cyano-5-dicyanomethylidene-2-oxo-2, 5-dihydrapyrrole m-p.l8Q°C; Amax (CH2Cl:) S62nm (s max 60231) ; M/Z (HI) 415 (M\ 20%) ,
15 400 (15), 372 (12), 344 (100), 283 (33) and 272 (25).
Examples 3-4 Preparation of Mixtures Exams 1 -? 3
20 A mixture of 34.3 pares of Component (All , wherein
Rx is methyl, and 5.75 pares of Component (Bl) is prepared by mixing the cwo dyes togecher and milling them as a 40% aqueous slurry with 20 pares of a high temperature stable dispersing agent until the dye
25 particle size (mean diameter) is in the range of 0.1 - 5 microns.
This dispersion is standardised to a liquid brand containing 20.5% of the mixture, by the addition of S.5 30 parts of a humectant and water (to 100 parts). This liquid is especially suitable for use in the direct

WO 00/32697

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printing and continuous dyeing of polyester and polyester/cellulose blends and can also be used for exhaust dyeing.
5 The same dispersion is standardised to a solid brand
containing 41% of the mixture and 59% dispersing agent, by the addition of the 39-parts of a temperature stable dispersing agent and drying to either a grain or powder form in a spray dryer. This product is especially 10 suitable for the exhaust dyeing of polyester,
polyester/cellulose and polyester/wool blends and can also be used for continuous dyeing and direct printing.-
A dyebath for the exhaust dyeing of polyester in 15 piece form is prepared by adding 3 mis of an aqueous
dispersion of the solid brand (Ig dye in 10 0 ml water at 40-50°C) to 55.8 ml of de-ionised water and 1.2 ml of buffer solution. To this dyebath is added a 5g piece of polyester and the whole is held for 45 minutes at 130°C 20 in a Warner Mathis Labomat high temperature dyeing machine. After rinsing with water and a reduction clearing treatment, the material is dyed a bright reddish blue shade which apoears almost identical when viewed under both normal daylight and tungsten light sources. 25
Example 4
A mixture of 19.7 parts of Component (A2) and 12.17
parts of Component (Bl) is prepared by mixing the two
30 dyes together and milling them as a 40% aqueous slurry
with 2 0 parts of a high temperature stable dispersing agent until the dye particle size (mean diameter) is m the range 0.1-5 microns.
35 The dispersion is standardised to a solid brand
containing 31.9% of the mixture and 63.1% dispersing

WO 00/32697

PCT/G 899/04026

agent, by the addition of 4a.1 parts of a high temperature stable dispersion agent and drying to either a grain or powder form in a spray dryer. This product is especially suitable for the exhaust dyeing of polyester, polyester/cellulose and polyester/wool blends and can also be used for continuous dyeing and direct printing.
A dyebath for the exhaust dyeing of polyester in piece form is prepared by adding 3 mis cf an aqueous dispersion of the solid brand (Ig dye in 100 ml water at 40-50°CJ to 55.3 ml of de-ionised water and 1.2 ml of buffer solution. To this dyebath is added a 5g piece of polyester and the whole is held for 45 minutes at 13 0°C in a Werner Mathis Labomat high temperature dyeing machine. After rinsing with water and a reduction clearing treatment, the material is dyed a bright reddish blue shade which appears almost identical when viewed under both rorm.ai daylight and tungsten light sources.

WE CLAIM:
1. A dye mixture comprising
(A) at least one monoazo dye of the formula (I)

en

wherein

X4 is CI, Br, I, CN or N02;
RA is C1-4 alkyl or NHCOQ, where Q is C i-4 alkyl;

and
each of RA1 and RA2, independently, is C i-4alkyl, C 2-4 alkenyl, C M4alkoxy-Ci-4alkyl, aryl-Ci-4; alkyl or aryloxy- Ci-4alkyl; and
(B) at least one pyrroline type dye of the formula (II).

(ID

wherein RB1 is H, C 1.20 alkyl or C 2-20 alkenyl; and D is aryl.
2. A dye mixture as claimed in claim 1, wherein, in a dye of the formula (I) of the mixture, XA; is Br or CN, RA is NHCOCH3, NHCOC2H5 CH3 or C2H5 and each or RA1 and RA2, independently is methyl, ethyl or allyl.

3. A dye mixture as claimed the formula (II) of the mixtui
wherein each of RB2 and R B3 independently is alkyl,. cycloalkyl, aryl, alkenyl or aralkyl.
4. A dye, mixture as claimed in claim 3, wherein D is a group of the formula (a), RB2 is as defined in claim 3 and RB3 is optionally substituted C 7-20 alkyl.
5. A dye mixture as claimed in claim 4, wherein R B1 is H, R B2 is H, R B2is C4H9 and RB2 is 1-methyl-n-hexyl.
6. A dye mixture as claimed in claim 5, wherein component (B) is a pyrroline type dye (B1) of the formula (II) wnerein:R B1 is H R B2 is C4H9 and RB3 is 1-methyl-n-hexyl or is a mixture of the pyrroline-type dye (B1) with a pyrroline-type dye (B2) of the formula (II), wherein RB1 is H, and each of R B2 and R B3 is C4Hg, which pyrroline type dye mixture contains up to 10%, by weight of the total weight of the pyrroline-type dye mixture, of the dye (B2).
7. A dye mixture as claimed in claim 4, wherein component (B) is a
pyrroline-type dye (B3) or (B4), each of the formula (II), or is a mixture of
the dyes (B3) and (B4) which dye (B 3) is a dye wherein R B1 is H, R B2 is
ethyl and R B3 is n- octyl and which dye (B4) is a dye wherein R B1 is H, R
B2 is ethyl and RB2 is 2-ethyl and RB3 is 2-ethyl-n-hexyl.
8. A dye mixture as claimed in claim 3, wherein D is a group of the formula (a), RB2 is as defined in claim 3 and RB3 is optionally substituted C1-6 alkyl.
9. A dye mixture as claimed in claim 7, wherein RB1 is H or alkyl, RB2 is 3 -phenyl-n-propyl and R B3 is C4H9.

10. A dye mixture as claimed in claim 1, wherein the ratio, by weight, of dye (I): dye (II) is from 95:5 to 30:70.
11. A dye mixture as claimed in claim 10, wherein the said ratio is from 85:15 to 35:65.

12. A dye mixture as claimed in claim 11, wherein the said ratio is from 70:30 to 40:60.
13. A dye mixture as claimed in claim 1, which comprises, as component (A), a monoazo dye (Al) of the formula (I) wherein XA is Br, RA is NHCOQ, where Q is CH3 or C2H5 or a mixture of monoazo dyes (Al1) and (Al2) each of the formula (I) wherein, in each dye, XA is Br, in dye (All) RA IS NHCOCH3 and in dye (AP) RA is NHCOC2H5; and, as component (B), at least a pyrroline type dye (Bl) of the formula (II), wherein RB1 is Hand D is a group of the formula

9
GH(CH3HCH2|4CH3

and optionally additionally up to 10% inclusive by weight of the total component (B) of a pyrroline type dye (B2) of the formula (II), wherein RB1 is H and D is a group of the formula

14. A dye mixture as claimed in claim 13, wherein the weight ratio of component (A): component (B) is from 90:10 to 80:20.
15. A dye mixture as claimed in claim 1, which comprises, as component (A), a monoazo dye (A2) of the formula (I), wherein X is CN, RA is CH3, and each of RA1 and RA2 is ethyl and as component (B), at least a pyrroline type dye (Bl) of the formula (II), wherein RB1 is H and D is a group of the formula
CH{CH3HCH2)4CH3
and optionally additionally up to 10% inclusive by weight of the total component (B) of a pyrroline type dye (B2) of the formula (II), wherein R R RB 2 is H and D is a group of the formula

16. A dye as claimed in claim 15, wherein the weight ratio of component (A): component (B) is from 70:30 to 55:45.
17. A dye mixture as claimed in claim 1, which comprises, as component (A), a monoazo dye (A3) of the formula (I), wherein XA is CN, RA is CH3, RA1 is CH3 and R RA2 is 3-phenyl-n-propyl and as component (B), at least a pyrroline type dye (Bl) of the formula (II), wherein RB1 is Hand D is a group of the formula

and optionally additionally up to 10% inclusive by weight of the total component (B) of a pyrroline type dye (B2) of the formula (II), wherein RB1 is H and D is a group of the formula

18. A dye mixture as claimed in claim 13, wherein the weight ratio of component (A): component (B) is from 70:30 to 55:45.
19. A composition comprising a dye mixture as claimed in anyone of the preceding claims and at least one dispersing agent, surfactant or wetting agent.
20. A process for colouring a synthetic textile material or fibre blend thereof, which comprises applying thereto a dye mixture as claimed in anyone of claims 1 to 19.
21. A process for colouring a synthetic textile material or fiber blend thereof, which comprises applying thereto a composition as claimed in claim 21, dispersed in an aqueous medium.
22. A process as claimed in claim 21 or claim 22, wherein the synthetic textile material or fiber blend thereof is a polyester or polyester-cellulose or polyester-wool blend.
Dated this December 4, 2000.
(RANJANA MEHTA DUTT)
OF REMFRY AND SAGAR ATTORNEY FOR THE APPLICANTS

Documents:

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in-pct-2000-00693-mum-assignment(14-9-2005).pdf

in-pct-2000-00693-mum-cancelled pages(5-11-2004).pdf

in-pct-2000-00693-mum-claims(granted)-(5-11-2004).doc

in-pct-2000-00693-mum-claims(granted)-(5-11-2004).pdf

in-pct-2000-00693-mum-correspondence(14-9-2005).pdf

in-pct-2000-00693-mum-correspondence(ipo)-(9-5-2003).pdf

in-pct-2000-00693-mum-form 1(4-12-2000).pdf

in-pct-2000-00693-mum-form 1a(5-11-2004).pdf

in-pct-2000-00693-mum-form 2(granted)-(5-11-2004).doc

in-pct-2000-00693-mum-form 2(granted)-(5-11-2004).pdf

in-pct-2000-00693-mum-form 3(4-12-2000).pdf

in-pct-2000-00693-mum-form 3(5-11-2004).pdf

in-pct-2000-00693-mum-form 4(29-7-2004).pdf

in-pct-2000-00693-mum-form 5(4-12-2000).pdf

in-pct-2000-00693-mum-form 6(14-9-2005).pdf

in-pct-2000-00693-mum-form-pct-ipea-409(4-12-2000).pdf

in-pct-2000-00693-mum-form-pct-isa-210(4-12-2000).pdf

in-pct-2000-00693-mum-petition under rule 137(5-11-2004).pdf

in-pct-2000-00693-mum-petition under rule 138(5-11-2004).pdf

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Patent Number

211109

Indian Patent Application Number

IN/PCT/2000/00693/MUM

PG Journal Number

45/2007

Publication Date

09-Nov-2007

Grant Date

17-Oct-2007

Date of Filing

04-Dec-2000

Name of Patentee

DYSTAR TEXTILFARBEN GMBH & CO., DEUTSCHLAND KG.

Applicant Address

INDUSTRIEPARK HOCHST, GEBAUDE B 598, 65926 FRANKFURT, GERMANY

Inventors:

#	Inventor's Name	Inventor's Address
1	ALAN THOMAS LEAVER	12 EGERTON ROAD, ECCLES, MANCHESTER M30 9LR, UNITED KINGDOM
2	DAVID BRIERLEY	3 TURFLAND AVENUE, ROYTON, OLDHAM OL2 6EL,

PCT International Classification Number

C09B67/22

PCT International Application Number

PCT/GB99/04026

PCT International Filing date

1999-12-02

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	9826659.6	1998-12-03	U.K.