Reactive colorants, mixtures of reactive colorants and production and use thereof

The present invention relates to novel reactive colorants and mixtures of reactive colorants, to processes for their production and to their use.

The practice of dyeing using reactive dyes has recently led to higher demands being made of the quality of the dyeings and the profitability of the dyeing process. As a result, there is still a need for novel reactive dyes having improved properties, especially in respect of their application.

Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixing. The known dyes do not satisfy these requirements in all properties.

The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel improved reactive dyes and mixtures of reactive dyes that possess the qualities characterised above to a high degree. The novel dyes and dye mixtures should especially be distinguished by high fixing yields and high fibre-dye binding stability; it should also be possible for dye that is not fixed to the fibre to be washed off easily. The dyes should also yield dyeings having good allround properties, for example fastness to light and to wetting.

It has been shown that the problem posed is largely solved by the novel dyes and dye mixtures defined below.

The present invention accordingly relates to dyes of formula (1)

wherein

R 1 and R 2 are each independently of the other hydrogen or C 1 -C 4 alkyl, and

D 1 and D 2 are each independently of the other a radical of formula (2)

wherein

(R 3 ) 0-3 denotes from 0 to 3 identical or different substituents selected from the group halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, nitro and sulfo, and

X 1 is a radical of formula (3a), (3b), (3c), (3d), (3e) or (3f)

—SO 2 —Z  (3a),

—NH—CO—(CH 2 ) m —SO 2 —Z  (3b),

—CONH—(CH 2 ) n —SO 2 —Z  (3c),

—NH—CO—CH(Hal)—CH 2 —Hal  (3d),

—NH—CO—C(Hal)═CH 2   (3e) or

wherein

Y is halogen, T independently thereof has a meaning given for Y or is a non-fibre-reactive substituent or is a fibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e)

—NH—(CH 2 ) 2-3 —SO 2 —Z  (4a),

—NH—(CH 2 ) 2-3 —O—(CH 2 ) 2-3 —SO 2 —Z  (4b),

wherein

Z is vinyl or a radical —CH 2 —CH 2 —U and U is a group removable under alkaline conditions,

Z′ is a group —CH(Hal)—CH 2 —Hal or —C(Hal)═CH 2 ,

m and n are each independently of the other the number 2, 3 or 4, and

Hal is halogen.

As C 1 -C 4 alkyl for R 1 and R 2 , each independently of the other, there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, especially methyl and ethyl.

Preferably, one of the radicals R 1 or R 2 is hydrogen and the other is methyl or ethyl.

Special preference is given to R 1 and R 2 as hydrogen.

As halogen for R 3 there come into consideration, for example, fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, and especially chlorine.

As C 1 -C 4 alkyl for R 3 there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, preferably methyl and ethyl, and especially methyl.

As C 1 -C 4 alkoxy for R 3 there come into consideration, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy, preferably methoxy and ethoxy, and especially methoxy.

Preferably, T is a non-fibre-reactive substituent or is a fibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e).

If T is a non-fibre-reactive substituent, it may be, for example, hydroxy; C 1 -C 4 alkoxy; unsubstituted or hydroxy-, carboxy- or sulfo-substituted C 1 -C 4 alkylthio; amino; amino mono- or di-substituted by C 1 -C 8 alkyl, wherein the alkyl is unsubstituted or is further substituted, e.g. by sulfo, sulfato, hydroxy, carboxy or by phenyl, especially by sulfo or by hydroxy and is uninterrupted or interrupted by an —O— radical; cyclohexylamino; morpholino; N—C 1 -C 4 alkyl-N-phenylamino or phenylamino or naphthylamino, wherein the phenyl or naphthyl is unsubstituted or substituted, e.g. by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, sulfo or by halogen.

Examples of suitable non-fibre-reactive substituents T include amino, methylamino, ethylamino, β-hydroxyethylamino, N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino, morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or 4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or 4-sulfophenylamino, disulfophenylamino, 2-, 3- or 4-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.

As non-fibre-reactive radical, T is preferably C 1 -C 4 alkoxy, unsubstituted or hydroxy-, carboxy- or sulfo-substituted C 1 -C 4 alkylthio, hydroxy, amino, N-mono- or N,N-di-C 1 -C 4 -alkylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or by sulfo, morpholino, or phenylamino or N—C 1 -C 4 alkyl-N-phenylamino (wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato) wherein the phenyl ring is in each case unsubstituted or substituted by sulfo, carboxy, acetylamino, chlorine, methyl or by methoxy, or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups.

Especially preferred non-fibre-reactive radicals T are amino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino, N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino or N—C 1 -C 4 alkyl-N-phenylamino.

In the case of the fibre-reactive radicals T of formulae (4a) and (4b), Z is preferably β-chloroethyl. In the case of the fibre-reactive radicals T of formulae (4c) and (4d), Z is preferably vinyl or β-sulfatoethyl.

If T is a fibre-reactive radical, T is preferably a radical of formula (4c) or (4d), and especially of formula (4c).

Hal in the fibre-reactive radicals of formulae (3d), (3e) and (4e) is preferably chlorine or bromine, especially bromine.

Y in the fibre-reactive radical of formula (3f) is, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine, and especially chlorine.

As a leaving group U there come into consideration, for example, —Cl, —Br, —F, —OSO 3 H, —SSO 3 H, —OCO—CH 3 , —OPO 3 H 2 , —OCO—C 6 H 5 , —OSO 2 —C 1 -C 4 alkyl and —OSO 2 —N(C 1 -C 4 alkyl) 2 . U is preferably a group of formula —Cl, —OSO 3 H, —SSO 3 H, —OCO—CH 3 , —OCO—C 6 H 5 or —OPO 3 H 2 , especially —Cl or —OSO 3 H, and more especially —OSO 3 H.

Examples of suitable radicals Z accordingly include vinyl, β-bromo- or β-chloroethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl, β-sulfatoethyl and β-thiosulfatoethyl. Z is preferably vinyl, β-chloroethyl or β-sulfatoethyl.

D 1 and D 2 preferably are each independently of the other a radical of formula (2a), (2b), (2c), (2d) or (2e)

especially of formula (2a) or (2e), wherein

(R 3a ) 0-2 denotes from 0 to 2 identical or different substituents selected from the group halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and sulfo, especially methyl, methoxy and sulfo,

X 1a is α,β-dibromopropionylamino or α-bromoacryloylamino,

m is the number 2 or 3, especially 3,

n is the number 2 or 3, especially 2, and

Z 1 , Z 2 , Z 3 and Z 4 are each independently of the others vinyl, β-chloroethyl or β-sulfatoethyl.

Z 1 and Z 2 are preferably each independently of the other vinyl or β-sulfatoethyl.

Z 3 is preferably β-chloroethyl or β-sulfatoethyl, especially β-chloroethyl.

Z 4 is preferably β-chloroethyl or β-sulfatoethyl, especially β-sulfatoethyl.

Preference is given to dyes of formula (1) wherein

D 1 and D 2 are each independently of the other a radical of formula (2a), (2b), (2c), (2d) or (2e), preferably of formula (2a) or (2e), and

R 1 and R 2 are hydrogen.

The radicals D 1 and D 2 in the dyes of formula (1) are identical or not identical.

The present invention relates also to a process for the preparation of dyes of formula (1), wherein

(i) approximately 1 molar equivalent of an amine of formula (5a)

D 1 —NH 2   (5a)

is diazotised in customary manner and reacted with approximately 1 molar equivalent of a compound of formula (6)

to form the compound of formula (7a)

and

(ii) approximately 1 molar equivalent of an amine of formula (5b)

D 2 —NH 2   (5b)

is diazotised in customary manner and reacted with approximately 1 molar equivalent of the compound of formula (7a) obtained according to (i), to form the compound of formula (1) wherein the definitions and preferred meanings given above for each of D 1 , D 2 , R 1 and R 2 apply.

The diazotisation of the amines of formulae (5a) and (5b) is carried out in a manner known per se, for example with a nitrite, e.g. with an alkali metal nitrite, such as sodium nitrite, in a mineral acid medium, e.g. in a hydrochloric acid medium, at temperatures of, for example, from −5 to 40° C., preferably from 0 to 20° C.

Coupling to the coupling components of formulae (6) and (7a) is carried out in a manner known per se, at acid, neutral or weakly alkaline pH values, for example at a pH value of from 0 to 8, and at temperatures of, for example, from −5 to 40° C., preferably from 0 to 30° C.

The first coupling (i) is effected in an acid medium, for example at a pH value of from 0 to 4, and the second coupling (ii) is effected at a higher pH value, in a weakly acid, neutral or weakly alkaline medium, for example at a pH value of from 4 to 8.

If the same procedure as described above is used, except that, instead of using 1 molar equivalent of an amine of formula (5a) and 1 molar equivalent of an amine of formula (5b), there are used in each of the process steps (i) and (ii) approximately 1 molar equivalent of a mixture of at least two, but preferably two, non-identical amines, for example a 1:1 molar mixture of the compounds of formulae (5a) and (5b), there are then obtained first, according to (i), a mixture of the compounds of formulae (7a) and (7b)

and, on further reaction of the mixture of the compounds of formulae (7a) and (7b), according to (ii), a mixture of dyes of formulae (1a), (1b), (1c) and (1d)

The present invention accordingly relates also to dye mixtures comprising at least one dye of formulae (1a) and (1b) together with at least one dye of formulae (1c) and (1d), especially one dye of each of formulae (1a), (1b), (1c) and (1d), wherein the definitions and preferred meanings given above for each of D 1 , D 2 , R 1 and R 2 apply and D 1 and D 2 are not identical.

Preferably, in the dye mixtures according to the invention, D 1 is a radical of formula (2a*)

and D 2 is a radical of formula (2a**)

wherein

R 3b and R 3c are each independently of the other hydrogen, methyl or methoxy, especially hydrogen, and

Z 1a and Z 1b are each independently of the other vinyl or β-sulfatoethyl, especially β-sulfatoethyl, and

R 1 and R 2 are hydrogen.

The ratio of the dyes of formulae (1a), (1b), (1c) and (1d) in the mixture can vary within wide ranges and will depend upon the ratio of the amines D 1 —NH 2 and D 2 —NH 2 used according to each of (i) and (ii).

The dye mixtures mentioned above contain, for example, from 5 to 95% by weight, especially from 10 to 90% by weight, and more especially from 20 to 80% by weight, of a dye of formula (1a) and/or (1b), based on the total amount of the dyes of formulae (1a), (1b), (1c) and (1d) in the mixture.

The compounds of formulae (5a), (5b) and (6) are known or can be obtained in a manner known per se.

The present invention relates also to dye mixtures comprising at least one dye of formula (1) together with at least one dye of formula (8)

wherein

r and s are each independently of the other the number 0 or 1 and

X 2 and X 3 are each independently of the other a radical of formula (3a), (3b), (3c) or (3d)

—SO 2 —Z  (3a),

—CONH—(CH 2 ) n —SO 2 —Z  (3b),

—NH—CO—CH(Hal)—CH 2 —Hal  (3c)

or

—NH—CO—C(Hal)═CH 2   (3d),

and

n is the number 2, 3 or 4,

Hal is halogen and

Z is vinyl or a radical —CH 2 —CH 2 —U and U is a group removable under alkaline conditions.

The definitions and preferred meanings given above for each of n, Hal and U apply.

The reactive dyes of formulae (1) and (8) contain sulfo groups, which may in each case be present either in the form of the free sulfo acid or, preferably, in the form of a salt thereof, for example in the form of a sodium, lithium, potassium or ammonium salt or in the form of a salt of an organic amine, e.g. in the form of a triethanolammonium salt.

The reactive dyes of formulae (1) and (8) and accordingly the dye mixtures may also comprise further additives, for example sodium chloride or dextrin.

Instead of the dye of formula (1), the dye mixtures according to the invention preferably comprise the above-mentioned mixtures of at least one dye of formulae (1a) and (1b) together with at least one dye of formulae (1c) and (1d), especially a compound of each of formulae (1a), (1b), (1c) and (1d), wherein the definitions and preferred meanings given above for the radicals D 1 , D 2 , R 1 and R 2 in the compounds of formulae (1a), (1b), (1c) and (1d) apply.

The dye of formula (8) in the dye mixture according to the invention is preferably a dye of formula (8a), (8b) or (8c)

especially of formula (8a),

wherein

one of the substituents G 1 and G 2 is amino and the other is hydroxy,

X 2a , X 3a and X 3b are each independently of the others β-sulfatoethylsulfonyl or vinylsulfonyl and

X 2b , X 2c and X 3c are each independently of the others α,β-dibromopropionylamino or α-bromoacryloylamino.

Especially preferred dye mixtures according to the invention comprise a compound of each of formulae (1a), (1b), (1c) and (1d) together with a dye of formula (8a).

The dye of formula (1) or the dyes of formulae (1a), (lb), (1c) and (1d) are present in the dye mixture according to the invention in a weight ratio with respect to the dye of formula (8) of, for example, from 1:99 to 99:1, preferably from 5:95 to 95:5, and especially from 10:90 to 90:10.

The dye mixtures according to the invention may be prepared, for example, by mixing the individual dyes. The mixing process is carried out, for example, in a suitable mill, e.g. a ball or pin mill, and also in a kneader or mixer.

The dye mixtures according to the invention may comprise, in addition to the reactive dyes mentioned above, further dyes, especially further reactive dyes for shade adjustment.

The dyes and dye mixtures according to the invention are fibre-reactive, that is they are capable of reacting with the hydroxyl groups of cellulose or with the reactive centres of natural and synthetic polyamides, with the formation of covalent chemical bonds.

The reactive dyes according to the invention and the mixtures of reactive dyes according to the invention are suitable for dyeing and printing a wide variety of materials, especially hydroxyl-group-containing or nitrogen-containing fibre materials. Examples include silk, leather, wool, polyamide fibres and polyurethanes, and especially all types of cellulosic fibre materials. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, and cellulose and regenerated cellulose. The dyes and dye mixtures according to the invention are also suitable for dyeing or printing hydroxyl-group-containing fibres contained in blend fabrics, for example blends of cotton and polyester fibres or polyamide fibres.

The dyes and dye mixtures according to the invention can be applied to the fibre material and fixed to the fibre in a number of ways, especially in the form of aqueous dye solutions or dye print pastes. They are suitable for the exhaust process and also for dyeing using the pad-dyeing process, can be used at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixing are high and unfixed dye can be washed off readily, the difference between the degree of exhaust and the degree of fixing being remarkably small, that is to say the soaping loss is very small. The dyes and dye mixtures according to the invention are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics containing wool.

The dyeings and prints produced on cellulose fibre materials using the dyes and dye mixtures according to the invention have a high tinctorial strength and a high fibre-dye binding stability in both acidic and alkaline ranges, and they also have good fastness to light and very good wet-fastness properties, such as fastness to washing, water, seawater, cross-dyeing and to perspiration, as well as good fastness to pleating, to pressing, to rubbing, and especially to chlorine.

The following Examples serve to illustrate the invention. The temperatures are given in degrees Celsius, parts are parts by weight, and the percentages relate to percent by weight, unless otherwise indicated. Parts by weight relate to parts by volume in a ratio of kilograms to liters.