The present invention relates to a process for the bichromatic and/or 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. However, it is possible to achive some shades by mixing only two colorants selected from a suitable yellow- or orange-, red- and blue-dyeing dye which is here called bichromatic dyeing.

Trichromatic and bichromatic dyeing is well known from the literature for various dye classes, for example from EP 83299, DE 2623178, EP 226982 and EP808940.

Optimum trichromatic or bichromatic 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 or bichromatic performance.

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

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

and at least one yellow-dyeing compound or orange-dyeing compound or one blue- dyeing compound.

In a further embodiment this object is achieved by a trichromatic dyeing process which is characterized by using a dye mixture comprising a red-dyeing compound of the formula (I) and at least one yellow-dyeing compound 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-dyeing compounds or orange-dyei ng compounds for the inventive trichromatic or bichromatic 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)

(0 (ia)

wherein X is a halogen radical and Y signifies -CH=CH2 or -CH2CH2-Z, wherein Z is a radical which can be eliminated by alkali, R6 and R7 signify independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl, B signifies

(ϋ) (iii)

wherein R8 signifies Ci^alkyl; -NH2 or -NHC1-4alkyl,

and the asterisk marks the bond to the -N=N- group. A suitable radical Z which can be eliminated by alkali or under alkaline conditions, respectively, is for example chlorine; bromine or -OSO3H or -SSO3H or the alkali metal salt thereof; and by preference -OSO3H or the alkali metal salt thereof.

Further suitable yellow-dyeing compounds or orange-dyeing compounds for the inventive trichromatic or bichromatic process have the following formula (IV)

wherein R13 signifies H; methyl; methoxy, ethoxy; -NHCONH2 or -NHCOCH3, R14 signifies H; methyl; methoxy or ethoxy, RG signifies

wherein R15 signifies H or chlorine, Y signifies -CH=CH2 or -CH2CH2-Z, wherein Z is a radical which can be eliminated by alkali, and may be bonded in the position 4 or 5 with respect to the azo group.

Suitable blue-dyeing compounds for the inventive trichromatic or bichromatic process have the following formula (V) or (Vl)

in which

each of R22 and R24 is independently H; -COOH; -SO3H; -NHCOCH3; -NHCOCHY2- CH2Yi; -NHCOCY2=CH2 or -NHCOCH2Y1,

Yi is chlorine; bromine; -OSO3H or -SSO3H and Y2 is H; chlorine or bromine.

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

in which Y signifies -CH=CH2 or -CH2CH2-Z, wherein Z is a radical which can be eliminated by alkali, R25 signifies H or -SO3H, R26 signifies H or -SO3H.

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

wherein each Y has independently from each other the same meanings as defined above R27 and R2β are independently from each other H; unsubstituted C1-4alkyl or substituted C1-4alkyl.

A preferred bichromatic dyeing process is characterized by using a dye mixture comprising a red-dyeing compound of the formula (I) and at least one yellow-dyeing compound or orange-dyeing compound of the formula (II), (III) and/or (IV)

A further preferred bichromatic dyeing process is characterized by using a dye mixture comprising a red-dyeing compound of the formula (I) and at least one blue-dyeing compound as per the formula (V), (Vl), and/or (VII).

A preferred trichromatic dyeing process is characterized by using a dye mixture comprising a red-dyeing compound of the formula (I) 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), (Vl), and/or (VII).

A more preferred trichromatic dyeing process is characterized by using a dye mixture comprising at least one yellow (or orange)-dyeing compound of formula (Ma), (lib) and/or (lie)

(Ha) (Hb) (Hc) wherein A is

and/or at least one yellow-dyeing compounds or orange-dyeing compounds of formula (IVa) or (IVb)

(IVa)

wherein RG is

and/or at least one blue-dyeing compound of formula (Va) or (Vb)

(Va) (Vb)

and/or at least one blue-dyeing compounds of formula (Via) or (VIb)

(Via) (VIb)

and/or at least one blue-dyeing compound of formula (Vila)

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.

Suitable groups Z which may be eliminated by alkali in the group -SO2-CH2CH2-Z are chlorine; bromine; -OSO3H or -SSO3H.

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.

The compound of the formula (I) is prepared according to EP962500.

The yellow-dyeing compounds 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. WO96/02593 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, WO0168775, 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 -4 Examples of yellow-dyeing compounds or orange-dyeing compounds of formula (II1) according to formula (II)

TABLE 2/ Examples 5-7 Examples of yellow-dyeing compounds or orange-dyeing compounds of formula (IV) according to formula (IV)

The application examples hereinbelow serve to illustrate the present invention. Parts are by weight and % are weight-%, unless otherwise indicated. 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 0C,

0.5 % (calculated on the fabric weight) of a red dye of formula (I) 0.8 % of a yellow dye as per Example 4 0.5 % of a blue dye as per Formula Va and

portions of 0.3, 0.7 and 1 g of sodium carbonate are added at 60cC 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 2-16 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 of formula (I) 0.4 % of a yellow dye as per Example 4 0.6 % of a blue dye as per Formula Va

APPLICATION EXAMPLE 3 (brown shade) 0.3 % of a red dye of formula (I) 0.9 % of a orange dye as per Example 6 0.6 % of a blue dye as per Formula V a

APPLICATION EXAMPLE 4 (olive shade) 0.1 % of a red dye of formula (I) 0.5 % of a yellow dye as per Example 6 0.6 % of a blue dye as per Formula Va

APPLICATION EXAMPLE 5 (brown shade) 0.5 % of a red dye of formula (I) 0.9 % of a yellow dye as per Example 4 0.3 % of a blue dye as per Formula Vila

APPLICATION EXAMPLE 6 (olive shade) 0.2 % of a red dye of formula (I) 0.4 % of a yellow dye as per Example 4 0.3 % of a blue dye as per Formula VIb.

APPLICATION EXAMPLE 7 (red shade) 0.2 % of a red dye of formula (I) 0.4 % of a yellow dye as per Example 4

APPLICATION EXAMPLE 8 (reddish orange shade) 0.3 % of a red dye of formula (I) 0.9 % of a orange dye as per Example 6 APPLICATION EXAMPLE 9 (orange shade) 0.1 % of a red dye of formula (I) 0.5 % of a yellow dye as per Example 6

APPLICATION EXAMPLE 10 (red orange shade) 0.5 % of a red dye of formula (I) 0.9 % of a yellow dye as per Example 4

APPLICATION EXAMPLE 11 (light orange shade) 0.2 % of a red dye of formula (I) 0.4 % of a yellow dye as per Example 4

APPLICATION EXAMPLE 12 (violet blue shade) 0.2 % of a red dye of formula (I) 0.6 % of a blue dye as per Formula V a

APPLICATION EXAMPLE 13 (violet blue shade) 0.3 % of a red dye of formula (I) 0.6 % of a blue dye as per Formula V a

APPLICATION EXAMPLE 14 (reddish blue shade) 0.1 % of a red dye of formula (I) 0.6 % of a blue dye as per Formula V a

APPLICATION EXAMPLE 15 (violet shade) 0.5 % of a red dye of formula (I) 0.3 % of a blue dye as per Formula Vila

APPLICATION EXAMPLE 16 (violet shade) 0.2 % of a red dye of formula (I) 0.3 % of a blue dye as per Formula Via.