TRICHROMATIC DYEING PROCESS AND DYE MIXTURES USED THEREIN The present invention relates to a process for the trichromatic dyeing or printing hydroxy-group-containing or nitrogen-containing organic substrates with dye mixtures and also to such dye mixtures and hydroxy-group-containing or nitrogen-containing organic substrates 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 EP808940.

Optimum trichromatic performance of any yellow (or orange), 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.

It is an object of the present invention to provide a trichromatic dyeing process and associated trichromatic dye mixtures consisting of at least one red component, at least one yellow (or orange) component and at least one blue component whereby trichromatic dyeing with good fastnesses is obtained.

This object is achieved by a trichromatic dyeing process which is characterized by using a dye mixture comprising at least one red-dyeing compound of the formula (I) wherein

R, is a C, 4-alkyl group or a substituted C24-alkyl group, R2 and R3 are independently from each other H;-OH ; -CN; Cl-2-alkyl ;-S03H ; -COOH; -OC, 2-alkyl or-NH2, X is a halogen radical and Y signifies-CH=CH2 or-CH2CH2-Z, wherein Z is a radical which can be eliminated by alkali, and at least one yellow (or orange) -dyeing compound; and at least one blue-dyeing compound.

Various auxiliaries, such as surface-active compounds, solubilising agents, thickeners, gel-forming substances, antioxidants, penetration agents, sequestering agents, buffers, light protection agents, care agents may additionally be present in the composition according to the invention.

Such auxiliaries are in particular wetting agents, antifoams, levelling agents, thickeners and plasticizers.

For the preparation of inks for printing processes suitable organic solvents or mixtures thereof are used. E. g. alcohols, ethers, esters, nitriles, carbonacidamides, cyclic amides, urea, sulfones and sulfone oxides.

Furthermore additional auxiliaries such as e. g. compounds, which adjust the viscosity and/or the surface tension, may be added to the ink composition.

Suitable yellow (or orange) -dyeing compounds for the inventive trichromatic process have the following formula (II) wherein R4 and R5 signify independently from each other H or-SO3H, A signifies a group of formula (i) or (ia)

wherein X and Y have the same meanings as defined above, R6 and R7 signify independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl, B signifies wherein R8 signifies C1. 4alkyl ;-NH2 or-NHC, 4alkyl, and the asterisk marks the bond to the-N=N-group.

Further suitable yellow (or orange) -dyeing compounds for the inventive trichromatic process have the following formula (III) wherein Rg signifies-S03H or-S02Y, wherein Y has the same definition as above, Rio signifies H or-S03H, R11 signifies H; unsubstituted C1-4alkyl or substituted C1-4alkyl, D signifies

(iv) (iva) () wherein X and Y have the same meanings as defined above and R12 signifies H; unsubstituted C, 4alkyl or substituted C1-4alkyl.

Further suitable yellow (or orange) -dyeing compounds for the inventive trichromatic process have the following formula (IV) wherein R, 3 signifies H; methyl ; methoxy, ethoxy ;-NHCONH2 or-NHCOCH3, R14 signifies H; methyl ; methoxy or ethoxy, RG signifies wherein R15 signifies H or chlorine, Y has the same definition as above and may be bonded in a meta-or in para- position with respect to the azo group.

Suitable blue-dyeing compounds for the inventive trichromatic process have the following formula (V) wherein R, 6 signify H or ;SO3H and R17 signifies wherein X and Y have the same meanings as defined above, Rig and Rig are independently from one another H; unsubstituted C1-4alkyl or substituted C, 4alkyl, n is 0 or 1, T signifies wherein R, 6 and Y have the meanings as defined above and R20 is H; unsubstituted C1-4alkyl or substituted C1-4alkyl.

Further suitable blue-dyeing compounds for the inventive trichromatic process have the following formula (VI)

in which R21 is H or-COOH, each of R22 and R24 is independently H;-COOH ; -SO3H ;-NHCOCH3 ;-NHCOCHY2- CH2Y, ; -NHCOCY2=CH2 or-NHCOCH2Y" R23-COOH, Y, is chlorine ; bromine ; -OSO3H or -SSO3H and Y2 is H; chlorine or bromine.

Further suitable blue-dyeing compounds for the inventive trichromatic process have the following formula (VII) in which Y has the same meanings as defined above, R25 signifies H or -OS3H, R26 signifies H or -SO3H.

Further suitable blue-dyeing compounds for the inventive trichromatic process have the following formula (VIII)

wherein each Y has independently from each other the same meanings as defined above R27 and R28 are independently from each other H; unsubstituted C,. 4alkyl or substituted C1-4alkyl.

A preferred trichromatic dyeing process is characterized by using a dye mixture comprising at least one red-dyeing compound of the formula (la) wherein X'isClorF, R', is a C12-alkyl, especially-C2H5, or a C24-alkyl group, which is monosubstituted by Cl, F, Br,-OH,-CN or-NH2, R'2 and R'3 are independently from each other H; C12-alkyl ; -SO3H or -OC1-2alkyl, especially H ;-CH3 ;-S03H or-OCH3 and the -SO2Y group is attached to the phenylring at position 3,4 or 5, wherein Y is as defined above and at least one yellow (or orange)-dyeing compound of the formula (II), (III) and/or (IV) and at least one blue-dyeing compound as per the formula (V), (VI), (Vil) and/or (VIII).

A more preferred trichromatic dyeing process is characterized by using a dye mixture comprising at least one yellow (or orange) -dyeing compound of formula (Ila), (Ilb) and/or (IIc) wherein A is and/or at least one yellow (or orange) -dyeing compounds of formula (illa) or (Illb) wherein D is and/or at least one yellow (or orange) -dyeing compounds of formula (IVa) or (IVb)

wherein RG is A more preferred trichromatic dyeing process is characterized by using a dye mixture comprising and/or at least one blue-dyeing compound of formula (Va), (Vb), (Vc), (Vd), (Ve) and/or (Vf) wherein T is

and/or at least one blue-dyeing compounds of formula (Vla) or (Vlb)

and/or at least one blue-dyeing compounds of formula (Vlla) or (Vllb) and/or at least one blue-dyeing compound of formula (Vllla) it is to be noted that all compounds may also be present in salt form. Useful salts in- clude 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.

Preferred hydroxy-group-containing or nitrogen-containing organic substrates are leather and fibrous materials, which comprise natural or synthetic polyamides and,

particularly, natural or regenerated cellulose such as, cotton, viscose and spun rayon.

The most preferred substrates are textile materials comprising cotton.

Compounds of the formula (I) are prepared by reacting a diazotized compound of the formula (1) wherein all substituents have the meanings as defined above, with a compound of the formula (2) wherein all substituents have the meanings as defined above.

The process is preferably carried out in an aqueous medium at a temperature of from 0 to 40°C, more preferably 0 to 25°C and at a pH of between 1 to 7, more preferably 1 to 6.

A dyestuff of formula (I) may be isolated in accordance with known methods, for example by salting out, filtering and drying optionally in vacuum and at slightly elevated temperature.

The yellow (or orange) -dyeing compounds are known from the state of the art and can therefore be produced according to the process given in the prior art. E. g. W09963995, W09963055 and F. Lehr, Dyes Pigm. (1990), 14 (4), 257.

The blue-dyeing compounds are also known from the state of the art and can therefore be produced according to the process given in the prior art. E. g. EP 99721, EP84314, W00168775, EP 149170, EP497174 and DE4241918.

This invention further provides dye mixtures for the trichromatic dyeing or printing of hydroxy-group-containing or nitrogen-containing organic substrates 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 30-65% by weight of the yellow (or orange) component according to the invention, 10-30% by weight of the red component according to the invention and 10-30% 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.

The same applies to the yellow (or orange) and blue components.

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 present invention further provides hydroxy-group-containing or nitrogen-containing organic substrates dyed or printed by a dye mixture according to the invention.

The process according to the invention provides dyeings and prints having a homo- geneous 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 fast-

nesses, which are in no way inferior to the fastness level of dyeings and prints with metal complexes, are obtained without aftertreatment. With an additional aftertreat- ment, 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 in the inventive trichromatic dyeing process.

TABLE 1/Examples 1-18 Examples of red-dyeing compounds of formula (Ib) according to formula (I)

Position Position of Ex. R1 R2 R3 X of -O2S- -SO3H 1-CH2CH3 Cl 2 3 3-CH2CH3 H H F 3 4 3-CH2CH3 H H F 4 4 3-CH2CH3 H H Ci 5 4 4 -CH2CH3 H H Cl 6 4 4-CH2CH3 H H F 7 4 3 -CH3 H H F 8 3 3-CH3 H H F _-CH2CH3 (2)-OCH3 Cl 10 4 3-CH2CH3 (2) -OCH3 (5)-CH3 Cl 11 4 3-CH3 (2) -OCH3 (5)-OCH3 F 12-CH2CH3 (2)-OCH3 (5)-OCH3 Cl 13 4 4 -CH2CH3 (2)-SO3H H Cl 14 5 3 -CH3 (2)-SO3H H F 15 5 3 -CH2CH3 (2)-SO3H H Cl 16 4 3 -CH2CH3 (2)-SO3H H Cl 17 4 3 -CH2CH3 (2)-SO3H H F 18 3 3 -CH2CH3 (4)-OCH3 H Cl

TABLE 2/Examples 19-35 Examples of red-dyeing compounds of formula (Ic) according to formula (I) Position Position of Ex. R1 R2 R3 X of-OzS--SOsH 19 3 4 -CH2CH3 H H Cl 20 3 3-CH2CH3 H H F 21 4 3-CH2CH3 H H F 22 4 3 -CH2CH3 H H Cl 23 4 4 -CH2CH3 H H Cl 24 4 4-CH2CH3 H H F 25 4 3-CH3 H H F 26 3 3-CH3 H H F 27-CH2CH3 (2)-OCH3 Cl 28 4 3 -CH2CH3 (2)-SO3H (5)-CH3 Cl 29 4 3-CH3 (2)-OCH3 (5)-OCH3 F 30 4 4 -CH2CH3 (2)-SO3H 95)-OCH3 Cl 31 4 4 -CH2CH3 (2)-SO3H H Cl 3E2 5 3 -CH3 (2)-SO3H H F 33 5 3 -CH2CH3 (2)-SO3H H Cl 34 4 3 -CH2CH3 (2)-SO3H H Cl 35 4 3 -CH2CH3 (2)-SO3H H F

TABLE 3/Examples 36-52 Examples of mixtures of red-dyeing compounds of formula (lb), (Ic), (Id) and (le) according to formula (I)

Position Position of Ex. R1 R2 R3 X of-02S--S03H 36-CH2CH3 Cl 37 3 3-CH2CH3 H H F 38 4 3-CH2CH3 H H F 39 4 3-CH2CH3 H H Cl 40 4 4 -CH2CH3 H H Cl 41-CH2CH3 F 42 4 3 -CH3 H H F 43 3 3-CH3 H H F 44 5 3 -CH2CH3 (2)-SO3H H Cl 45 4 3 -CH2CH3 (2)-SO3H (5)-CH3 Cl 46 4 3 -CH3 (2) -OCH3 (5)-OCH3 F 47 4 4 -CH2CH3 (2)-SO3H 95)-OCH3 Cl 48 4 4 -CH2CH3 (2)-SO3H H Cl 49 5 3 -CH3 (2)-SO3H H F 50 5 3 -CH2CH3 (2)-SO3H H Cl 51 4 3 -CH2CH3 (2)-SO3H H Cl 52 4 3 -CH2CH3 (2)-SO3H H F

TABLE 4/Examples 53-56 Examples of yellow (or orange) -dyeing compounds of formula (II') according to formula (II)

Position Ex. R4 Ru A - N=N- oh cl OH cl 0 0 53 S03H (3)-SO3H ! N v 2 H03S /H \N H OH Ci N I O . H 0 H F 55 H (4)-SO3H N non 3 F n 0 H H H O e , qNyllyN 56 S03H (3)-SO3H, 7 NtN 2 HNrNH2 C} T 0 TABLE 5/Examples 57-59 Examples of orange-dyeing compounds of formula (III') according to formula (III) Ex. Rg Rio D F -N N F nui _ 58 SO2CH2CH2OSO3H SO H ANtu"SSoso3H o,, o 'CH3 0 0 59 S02CH2CH2OSO3H S03H N-, Z'oso3H H H

TABLE 6/Examples 60-62 Examples of yellow (or orange) -dyeing compounds of formula (IV') according to formula (IV) Position Ex. G RG' -SO2CH2CH20SO3H F H N 60 4-NH2 N F F HAN 61 3-CH3 N F IF Non 62 ANiNk k N N"1 kO

TABLE 7 / Examples 63-72 Examples of blue-dyeing compounds of formula (V) Ex. Ri7 Rie T - 63 (4)-SO2CH2CH20S03H H 0,, P 64 (4)-SO2CH2CH20S03H H DT ' 65 (5)-SOzCH2CH20S03H-S03H 03H SO \ 66 N-S03H H03S0 N N N H 67 H03SO N 0,, P H /S'OS03H O O Fi (5) _ H3C t O 4J N H < O y H (5)- 69 N N-OSO, H Fez F p o 7O N H--SO3H H'S \\SOS03H H-S03H -Y) a 71 ! SsE OSO3H H-soh Cri (5)-cri F 72 J (H--SO. H s F I ci

The application examples hereinbelow serve to illustrate the present invention. Parts are by weight and temperatures are in degrees Celsius, unless otherwise indicated.

APPLICATION EXAMPLE 1 A 20 g sample of bleached cotton knitting. is transferred in a solution of 16 g sodium sulfate in 200 ml water at 60 °C, 0.5 % (calculated on the fabric weight) of a red dye as per Example 1 0.8 % of a yellow dye as per Example 55 0.5 % of a blue dye as per Formula Vla and portions of 0.3, 0.7 and 1 g of sodium carbonate are added at 60°C after 30,45 respectively 60 minutes. The temperature is maintained during another 60 minutes.

The dyed fabric is rinsed in hot distilled water during 2 minutes and in hot tap water during 1 minute. After being kept in 1000 ml distilled water at the boil for 20 minutes. the fabric is dried. It provides a brown cotton dyeing having good fastnesses.

EXAMPLES 2-6 These examples are made analogous to Use Example 1, but by using dyestuff mixtures as mentioned below. The resulted shade is given in brackets.

APPLICATION EXAMPLE 2 (olive shade) 0.2 % of a red dye as per Example 1 0.4% of a yellow dye as per Example 55 0.6 % of a blue dye as per Formula Via APPLICATION EXAMPLE 3 (brown shade) 0.3 % of a red dye as per Example 39 0.9 % of a orange dye as per Example 60 0.6 % of a blue dye as per Formula Vla APPLICATION EXAMPLE 4 (olive shade) 0.1 % of a red dye as per Example 39 0.5% of a yellow dye as per Example 60 0.6 % of a blue dye as per Formula Via APPLICATION EXAMPLE 5 (brown shade) 0.5 % of a red dye as per Example 2 0.9 % of a yellow dye as per Example 55 0.3 % of a blue dye as per Example 69 APPLICATION EXAMPLE 6 (olive shade) 0.2 % of a red dye as per Example 2 0.4% of a yellow dye as per Example 55 0.3 % of a blue dye as per Example 69.