Title of Invention	TRICHROMATIC DYEING PROCESS
Abstract	The present invention relates toa process for the trichromatic dyeing or printing of natural or sunthetic polymide fibres or such fibres as contain polymide with dye mixtures and also to such dye mixtures and polyamide fibres dyed or printed therewith.

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TRICHROMATIC DYEING PROCESS The present invention relates to a process for the trichromatic dyeing or printing of natural or synthetic polyamide fibres or such fibres as contain polyamide with dye mixtures and also to such dye mixtures and polyamide fibres dyed or printed therewith. Trichromatic describes the additive colour mixing of suitable yellow- or orange-, red-and blue-dyeing dyes with which any desired shade in the visible spectrum can be obtained by suitably selecting the amount ratios for the dyes. Trichromatic dyeing is well known from the literature for various dye classes, for example from EP 83299, DE 2623178, EP 226982 and EP 808940. Optimum trichromatic performance of any yellow, red and blue dye mixture is crucially dependent on the neutral affinity and migration characteristics. Dyes having identical or very similar characteristics with regard to neutral affinity and migration are highly compatible with regard to trichromatic performance. Combinations of dyes having good trichromatic properties are known for monosulphonated acid dyes. By contrast, no such dye mixtures are known to date for disulphonated acid dyes, for example the Nyiosan® F dyes from Clariant. It is an object of the present invention to provide a trichromatic dyeing process and associated trichromatic dye mixtures consisting of at least one blue component, at least one yellow component and at least one red component whereby trichromatic dyeing with good fastnesses is made possible even for disulphonated acid dyes. This object is achieved by a trichromatic dyeing process which is characterized in that it comprises using a dye mixture consisting of at least one blue-dyeing compound of the formula (I) where B is hydrogen; alkyl; hydroxy!-, alkoxy-, alkanoyloxy- or phenoxy-substituted alkyl, aralkyl, cycloalkyl or unsubstituted or alkyl-, halogen-, alkoxy-, nitro-, cyano-, alkoxycarbonyl-, carbamoyl- or sulphamoyl-substituted phenyl, R4 is hydrogen; alkyl of 1-8 carbon atoms which may be interrupted by oxygen atoms and may be substituted by hydroxyl, acyloxy, alkoxy, cyano, cyclo-alkoxy, aralkoxy or aroxy; unsubstituted or hydroxyl-, chlorine-, hydroxyalkyl-, chloroalkyl- or alkyl-substituted cycloalkyl or polycycioalkyl radicals of 5 to 15 carbon atoms; aralkyl radicals of 7 to 15 carbon atoms or unsubstituted or chlorine-, hydroxyl-, alkoxy-, alkyl-, hydroxyalkyl- or hydroxy-alkoxy-substituted phenyl radicals and also alkenyl, pyrrolidonylalkyl and carbonylalkyl radicals, RT is hydrogen; alkyl of 1-8 carbon atoms or hydroxyalkyl of 2 to 9 carbon atoms, and where R9 is chlorine; hydroxy! or NHCN, R10 is hydrogen; chlorine or cyano, Rn is hydrogen; Chalky!; hydroxyl-monosubstituted or -disubstituted C2-8alkyl, phenyl, phenyl(Ci^alkyl) or cyclohexyl and R12 is unsubstituted or halogen-substituted, hydroxyl-monosubstituted or -disubstituted, phenyl-substituted, carboxyl-substituted or d.^aikoxy-substituted C4.2oalkyl; -G-O-d.^alkyl, where G is do^lkylene; phenyl or phenyl(d-3alkyl), whose phenyl ring is unsubstituted or substituted by one to three substituents selected from the group consisting of halogen, d.i6alkyl, C2.6hydroxyalkyl, Ci.6alkoxy, phenoxy and -NHCOCH3; or is cyclohexyl which is unsubstituted or substituted by one to three d^alkyl groups, with the proviso that the total number of carbon atoms in Rn and R12 together is at Jeast 8, or where E represents an aromatic, araliphatic, hydroaromatic radical or two aromatic radicals, Z represents hydrogen or a discretionary substituent except sulphonic acid and carboxylic acid groups, n represents 1 or 2, and at least one anionic and/or nonionic dyeing auxiliary. A preferred trichromatic dyeing process comprises, as well as at least one anionic and/or nonionic dyeing auxiliary, using dye mixtures consisting of at least one blue-dyeing compound as per the formula (I) where A is a hydrogen atom or a discretionarily substituted alkyl or aryl radical, and at least one yellow-dyeing compound as per the formula (II) where B is hydrogen; alkyl; hydroxy!-, alkoxy-, alkanoyloxy or phenoxy-substituted alkyl, R4 is hydrogen or alkyl of 1-8 carbon atoms which may be interrupted by oxygen atoms and may be substituted by hydroxyl, acyloxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy, R2 is hydrogen; alkyl of 1-8 carbon atoms which may be interrupted by oxygen atoms and may be aryl radicals of 7 to 15 carbon atoms and Y is hydrogen; chlorine; bromine or -S03H, Yi is hydrogen; chlorine; bromine; methyl or -S03H, Y2 is hydrogen; chlorine; bromine; methyl or -S03H, and at least one red-dyeing compound as per the formula (III) where R9 is chlorine; hydroxy! or NHCN, R10 is hydrogen; chlorine or cyano, Ru is hydrogen; d^alkyl; hydroxyl-monosubstituted or-disubstituted C2-4alkyl or phenyl and Ri2 is unsubstituted or phenyl-monosubstituted C^alkyl; -G1-0-C6.i2alkyI, where G1 is linear C2-3alkylene; C6.i6alkyl- or phenoxy-monosubstituted phenyl; phenyl- (Ci.2alkyl) whose phenyl ring is unsubstituted or monosubstituted by C6.14alkyl; or cyclohexyl substituted by one to three methyl groups, and/or at least one red-dyeing compound of the formula (IVa) where Ri8 is hydrogen or substituted or unsubstituted C^alkyl, Rig independently has the same meanings as R18, n is 1 or 2. A further likewise preferred trichromatic dyeing process comprises, as well as at least one anionic and/or nonionic dyeing auxiliary, using dye mixtures whose red component is a mixture of at least one red component of the formula (III) and at least one red component of the formula (IV). A further likewise preferred trichromatic dyeing process comprises, as well as at least one anionic and/or nonionic dyeing auxiliary, using dye mixtures whose red component is a mixture of at least one red component of the formula (III) and at least one red component of the formula (V). A further likewise preferred trichromatic dyeing process comprises, as well as at least one anionic and/or nonionic dyeing auxiliary, using dye mixtures whose red component is a mixture of at least one red component of the formula (IV) and at least one red component of the formula (V). A more preferred trichromatic dyeing process comprises, as well as at least one anionic and/or nonionic dyeing auxiliary, using dye mixtures containing at least one blue-dyeing compound as per the formula (I), where A is a hydrogen atom and R is a discretionarily substituted aryl radical and at least one yellow-dyeing compound as per the formula (II) where B is hydrogen or methyl, R4 is hydrogen or alkyl of 1-4 carbon atoms, RT is hydrogen or alkyl of 1-4 carbon atoms, R2 is hydrogen; alkyl of 1-4 carbon atoms or aralkyl radicals of 7 to 15 carbon atoms, R3 is hydrogen or methyl Y is hydrogen or chlorine, Y, is hydrogen or chlorine, Y2 is hydrogen or -S03H, and at least one red-dyeing compound as per the formula (III) It is to be noted that all compounds may also be present in salt form. Useful salts include in particular alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine. It is likewise to be noted that the alkyl groups can be linear or branched. The individual dyes and their syntheses are described in the literature. Compounds of the formula (I) are prepared according to WO 99/5168, compounds of the formula (II) according to DE 2302582, compounds of the formula (III) according to DE 4209261, compounds of the formulae (IV) and (Va) according to DE 5565480 and compounds of the formula (V) according to GB 810246. This invention further provides dye mixtures for the trichromatic dyeing or printing of natural or synthetic polyamide fibre material or such polyamide-containing material which are used in the above processes according to the invention. The inventive process for trichromatic dyeing or printing can be applied to all customary and known dyeing and printing processes, for example the continuous process, the exhaust process, the foam dyeing process and the ink-jet process. The composition of the individual dye components in the trichromatic dye mixture used in the process according to the invention depends on the desired hue. For instance, a brown hue preferably utilizes 55-65% by weight of the yellow component according to the invention, 20-30% by weight of the red component according to the invention and 10-20% by weight of the blue component according to the invention. The red component, as described above, can consist of a single component or of a mixture of different red individual components which conform to the formulae (III), (IV) and (V). Preference is given to double and triple combinations. It is to be noted that the components of the individual red components of the formulae (III)-(V) can themselves be mixtures. When a red individual component consisting of only one red component of the formula (III) is used, its fraction should not exceed 50% by weight of the trichromatic colour mixture. When a red triple mixture consisting of one each of at least one red compound of the formula (III) and at least one red compound of the formula (IV) and at least one red compound of the formula (V), the fraction of the compounds of the formula (III) should not exceed 40% by weight based on the triple red mixture. The total amount of dyes in the process according to the invention is between 0.01 and 15% by weight, preferably between 1 and 10% by weight. The dye mixtures according to the invention, as well as the dyes and the water, further contain anionic or nonionic dyeing or printing auxiliaries. • Such auxiliaries are in particular wetting agents, antifoams, levelling agents, thickeners and plasticizers. The present invention further provides substrates consisting of natural or synthetic polyamide or polyamidic substrates dyed or printed by a dye mixture according to the invention. The process according to the invention provides dyeings and prints having a homogeneous hue build-up throughout the entire hue spectrum with on-tone exhaustion, with a high bath exhaustion even in the case of fibres with low saturation and with a high dye build-up on fine fibres, particularly on microfibres. The resulting dyeings or prints are notable for very high wet fastnesses, specifically the fastnesses in washing, perspiration and water. These good wet and fabrication fastnesses, which are in no way inferior to the fastness level of dyeings and prints with metal complexes, are obtained without aftertreatment. With an additional after-treatment, these fastnesses are even exceeded. These excellent results are provided by metal-free elements which meet the current and future ecological requirements of national institutes and regulations. The tables which follow show some examples of the individual components of the dye mixtures which are used together with the anionic or nonionic dyeing or printing auxiliary. 1.0% of an anionic oil sulphonate and 1.0 g/l of sodium acetate The pH is adjusted to 4.5 with acetic acid. The liquor is heated to 70°C at 2°C/min and subsequently dyed to 98°C with 0.8°C/min. This is followed by cooling after 30 min and rinsing on attainment of 70°C. Drying without aftertreatment with a fixative provides a level brown dyeing possessing high household wash, perspiration and water fastness. USE EXAMPLE 2 A 20 g wool fabric is dyed in a liquor ratio of 20:1 with the following additions: 0.32% of a yellow dye as per Example 5 0.06% of a red dye as per Example 13 0.06% of a red dye as per Example 16 0.06% of a red dye as per Example 7 0.5% of a blue dye as per Example 2 1.0% of an anionic oil sulphonate 1.0% of an anionic fatty amine polyglycol ether 1.0 g/l of sodium acetate The pH is adjusted to 4.5 with acetic acid. The dyeing operation corresponds to that of Example 1. It provides a grey wool fabric having good perspiration and water fastnesses. USE EXAMPLE 3 A 20 g 90/10 PA/elastomer blend is dyed and finished similarly to Use Example 1. The dyeing possesses very good wash and perspiration fastnesses. USE EXAMPLE 4 A PA carpet is padded to a 100% pick-up with the following liquor: 2.5 g/l of a yellow dye as per Example 5 0.36 g/l of a red dye as per Example 13 0.36 g/l of a red dye as per Example 16 0.18 g/l of a red dye as per Example 7 1.7 g/l of a blue dye as per Example 2 2.0 g/l of a polyglycol ether sulphonate 4.0 g/l of a commercially available thickener based on bean flour ether The pH is adjusted to 6 with acetic acid. The carpet is then printed with a print paste containing the following components: 20.0 g/kg of a commercially available cationic fatty acid alkyl amine 20.0 g/kg of a commercially available thickener based on bean flour ether whose pH has been adjusted to 8 with sodium carbonate. The coloured carpet is fixed in saturated steam for 5 min, rinsed and dried. The white/olive-green carpet obtained has very good wet fastnesses. USE EXAMPLE 5 Similar to Example 4 except for addition of 3 g/kg of Acid Yellow 49 in the print paste. The carpet obtained is olive green with a bright yellow print. USE EXAMPLE 6 A PA fabric is printed with the following printing batches: 0.2 g/kg of a yellow dye as per Example 5 1 -7 g/kg of a blue dye as per Example 2 0.6 g/kg of a red dye as per Example 13 0.6 g/kg of a red dye as per Example 16 03 g/kg of a red dye as per Example 7 10.0 g/kg of glycol ether 20.0 g/kg of urea 399.3 g/kg of boiling water 500.0 g/kg of bean flour ether thickener Printing is followed by 30 min of fixing with saturated steam at 102°C and then by rinsing and drying. The print obtained is violet and possesses high wet fastness. 1. Trichromatic dyeing process for dyeing or printing natural or synthetic polyamide fibres or such fibres as contain polyamide, characterized in that it comprises using a dye mixture consisting of at least one blue-dyeing compound of the formula (I) where A is a hydrogen atom or a discretionary substituent and R is a discretionarily substituted alkyl, cycloalkyl or aryl radical, and of at least one yellow-dyeing compound of the formula (II) where B is hydrogen; alkyl; hydroxy!-, alkoxy-, alkanoyloxy- or phenoxy-sub- stituted alkyl, aralkyl, cycloalkyl or unsubstituted or alkyl-, halogen-, alkoxy-, nitro-, cyano-, alkoxycarbonyl-, carbamoyl- or sulphamoyl- substituted phenyl, R4 is hydrogen; alkyl of 1-8 carbon atoms which may be interrupted by oxygen atoms and may be substituted by hydroxyl, acyloxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy; unsubstituted or hydroxy!-, chlorine-, hydroxyalkyl-, chloroalkyl- or alkyl-substituted cycloalkyl or polycycloalkyl radicals of 5 to 15 carbon atoms, aralkyl radicals of 7 to 15 carbon atoms or unsubstituted or chlorine-, hydroxyl-, alkoxy-, alkyl-, hydroxyalkyl- or hydroxyalkoxy-substituted phenyl radicals and also alkenyl, pyrrolidonylalkyl and carbonylalkyl radicals, Ri is hydrogen; alkyl of 1-8 carbon atoms or hydroxyalkyl of 2 to 9 carbon atoms, and R4 and R, combine with the nitrogen to form the radical of pyrrolidine, of piperidine or of morpholine and independently R2 has the same meanings as R4, R3 has the same meanings as R1 and R2 and R3 together have the same meanings as R4 and Ri together, Y is hydrogen; cyano; chlorine; bromine; methyl sulphone; ethyl sulphone; phenyl sulphone; carbalkoxy or-S03H, Yi is hydrogen; chlorine; bromine or-S03H Y2 is hydrogen; chlorine; bromine; methyl; carbalkoxy; 2-benzothiazolyl or-S03H, and where B, R, to R4 and Y to Y2 contain sulphonic acid groups, and of at least one red-dyeing compound of the formula (III) where each R13 is independently hydrogen, C1-4alkyl, halogen, Ru is hydrogen or substituted or unsubstituted C1-4alkyl, R15 independently has the same meanings as R14, or R14 and R15 combine to form a cycloaliphatic ring of 5-8 carbon atoms, R16 is hydrogen or hydroxy! and R117 independently has the same meanings as R16 and/or at least one red-dyeing compound of the formula (V) where E represents an aromatic, araliphatic, hydroaromatic radical or two aromatic radicals, Z represents hydrogen or a discretionary substituent except sulphonic acid and carboxylic acid groups, n represents 1 or 2, and at least one anionic and/or nonionic dyeing auxiliary. 2 Trichromatic dyeing process according to Claim 1, characterized in that it comprises using a dye mixture consisting of at least one blue-dyeing compound as per the formula (I) where A is a hydrogen atom or a discretionarily substituted aikyl or aryl radical, and of at least one yellow-dyeing compound as per the formula (II) where B is hydrogen; alkyl; hydroxyl-, alkoxy-, alkanoyloxy or phenoxy-substituted alkyl, R4 is hydrogen or alkyl of 1-8 carbon atoms which may be interrupted by oxygen atoms and may be substituted by hydroxyl, acyloxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy, R2 is hydrogen; alkyl of 1-8 carbon atoms which may be interrupted by oxygen atoms and may be aryl radicals of 7 to 15 carbon atoms and Y is hydrogen; chlorine; bromine or-S03H, Y2 is hydrogen; chlorine; bromine; methyl or -S03H, and of at least one red-dyeing compound as per the formula (III) where R9 is chlorine; hydroxyl or NHCN, R,o is hydrogen; chlorine or cyano, Rn is hydrogen; C1-4alkyl; hydroxyl-monosubstituted or-disubstituted C2.4aikyl; or phenyl and R12 is unsubstituted or phenyl-monosubstituted C4-14alky!; -G1-0-C6-12alkylT where G1 is linear C2.3alkylene; C6.16aikyl- or phenoxy-monosubstituted phenyl; phenyl(C1-2alkyl) whose phenyl ring is unsubstituted or monosub-stituted by C6„i4alkyl; or cyclohexyl substituted by one to three methyl groups, and/or of a red-dyeing compound of the formula (IVb) and/or of at least one red-dyeing compound of the formula (Va) where R18 is hydrogen or substituted or unsubstituted C1.4alkyl, R19 independently has the same meanings as R18l n is 1 or 2, and at least one anionic and/or nonionic dyeing auxiliary. * 3. Trichromatic dyeing process according to Claim 1 or 2, characterized in that it comprises using a dyeing mixture consisting of at least one blue-dyeing compound as per the formula (I), where A is a hydrogen atom and R is a discretionarily substituted aryl radical and of at least one yellow-dyeing compound as per the formula (II) where B is hydrogen or methyl, R4 is hydrogen or alkyl of 1-4 carbon atoms, R, is hydrogen or alkyl of 1-4 carbon atoms, R2 is hydrogen; alkyl of 1-4 carbon atoms or aralkyl radicals of 7 to 15 carbon atoms, R3 is hydrogen or methyl Y is hydrogen or chlorine, YT is hydrogen or chlorine, Y2 is hydrogen or -S03H, where R18 is hydrogen or/nethyl, R19 independently has the same meanings as R18 and at least one anionic and/or nonionic dyeing auxiliary. 4. Trichromatic dyeing process according to Claim 1 or 2, characterized in that it comprises using a dye mixture consisting of at least one blue component. according to Claim 1 or 2, and of at least one yellow component from Claim 1 or 2 and of a red component which constitutes a mixture of at least one compound of the formula (III) and at least one compound of the formula (IV), and at least one anionic and/or nonionic dyeing auxiliary. 5. Trichromatic dyeing process according to Claim 1 or 2, characterized in that it comprises using a dye mixture consisting of at least one blue component according to Claim 1 or 2, and of at least one yellow component from Claim 1 or 2 and of a red component which constitutes a mixture of at least one compound of the formula (III) and at least one compound of the formula (V), and at least one anionic and/or nonionic dyeing auxiliary. 6. Trichromatic dyeing process according to Claim 1 or 2, characterized in that it comprises using a dye mixture consisting of at least one blue component according to Claim 1 or 2, and of at least one yellow component from Claim 1 or 2 and of a red component which constitutes a mixture of at least one compound of the formula (IV) and at least one compound of the formula (V), and at least one anionic and/or nonionic dyeing auxiliary. 7. Dye mixtures used in the processes of Claims 1-6. Substrates consisting of natural or synthetic polyamide or polyamidic substrates dyed or printed by a trichromatic dyeing process as claimed in any of Claims 1-6. 9. A trichromatic dyeing process substantially as herein described and exemplified. 10 . A dye mixtures substantially as herein described and exemplified

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