WO2010094415A1

WO2010094415A1 - Fluorine containing reactive dyes

Info

Publication number: WO2010094415A1
Application number: PCT/EP2010/000799
Authority: WO
Inventors: Warren Ebenezer; Stefan Ehrenberg
Original assignee: Dystar Colours Deutschland GmbH
Current assignee: Dystar Colours Distribution GmbH
Priority date: 2009-02-18
Filing date: 2010-02-10
Publication date: 2010-08-26
Anticipated expiration: 2011-08-18
Also published as: CN102317378A; CN102317378B

Abstract

The present invention claims dyestuffs of the formula (I) wherein X¹, RG, R¹, R², Z¹, a, b and M are defined as given in claim 1, a method for their preparation and their use.

Description

DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG 2009/C001Ausl/Dr.My

Fluorine containing Reactive Dyes

This invention relates to the technical field of fibre-reactive azo dyes.

Dyestuffs and colorants, respectively, containing fluorine atoms in form of a trifluoromethyl group are known and described in literature. For example, GB732121 discloses monozo acid dyestuffs comprising a trifluoromethyl-benzenesulfonic acid. As regards fibre-reactive dyestuffs, trifluoromethyl groups are within the generic teaching of for example GB 2 259 710 A₁ EP 0 094 020 A1 , EP 0 354 409 A1 , EP 0 385426 A1 , EP 0 433 764 A1 , EP 470 930 A1 , EP 0 603 116 A1 and EP 0 872 523 A2. However, all these references lack any specific teaching of such dyestuffs. Monoazoanilide pigments which are ring fluorinated are described as well, see Dyes and Pigments 42 (1999) 159-172. Further, fibre-reactive triphendioxazine dyes carrying a fluorine atom at the triphendioxazine chromophor are described in WO 2007/077129 A2. Fibre-reactive dyes containing fluorine atoms are also disclosed in EP 0 167 785 A1 and EP 0 043 560 A1.

It has been surprisingly found that fibre-reactive dyestuffs containing fluorine atoms as defined below show particularly advantageous fastness profiles when reactively applied to cotton especially in relation to fastness to light, chlorine and perspiration light fastness and additionally exhibit very good levels of build up. Also, the dyestuffs give level shades with good contact fastness after wash off.

Accordingly, the present invention provides dyestuffs of the formula (I)

wherein R¹ is F or CF₃; Z¹ is -CH=CH₂ or -CH₂CH₂G wherein G is a alkali-eliminatable group; R² is hydrogen, (Ci-C₄)-alkyl, (C_rC₄)-alkoxy, hydroxy or chlorine; X¹ is an aromatic or heteroaromatic divalent group;

RG is a reactive group capable of forming a covalent bond to carboxamido- and/or hydroxyl-containing material under dyeing conditions or a group comprising a reactive group capable of forming a covalent bond to cellulose under dyeing conditions or is hydrogen; a is 0, 1 or 2; b is 1 in case R¹ is CF₃ and is 1 or 2 in case R¹ is F; and

M is hydrogen, an alkali metal or an equivalent of an alkaline earth metal.

Preferred aromatic or heteroaromatic divalent groups standing for X¹ correspond to one of the formulae (Ilia) to (IHk)

wherein

Ar is phenylen or phenylen which is substituted by 1 , 2 or 3 substituents selected from the group comprising (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, hydroxy, trifluormethyl, chlorine, fluorine and -SO₃M; E¹ has one of the meanings of Ar , is naphthyl or naphthyl which is substituted by 1 , 2 or 3 substituents selected from the group comprising (d-C₄)-alkyl, (C₁-C₄J-HIkOXy, - SO₃M, amino, acetylamino or hydroxy; or is a 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, or is a 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, which is substituted by 1 , 2 or 3 substituents selected from the group comprising (Ci-C₄)-alkyl and (CrC₄)-alkoxy; E² is phenylene or naphthylene which are unsubstituted or substituted by 1 , 2 or 3 substituents selected from the group comprising (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy -SO3M, amino, acetylamino or hydroxy; or is a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, or is a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, which is substituted by 1 , 2 or 3 substituents selected from the group comprising (Ci-C₄)-alkyl and (Ci-C₄)-alkoxy; or is a group of the formula (IV)

wherein

R⁷ is (CrC₄)-alkyl, (CrC₄)-alkoxy -SO₃M or hydroxy; R⁸ and R⁸' independently are hydrogen, (C_rC₆)-alkyl, sulfo-(CrC₆)-alkyl, phenyl or phenyl substituted by (Ci-C₄)-alkyl, (CrC₄)-alkoxy, hydroxyl, -SO₃M₁ halogen,

-COOM, acetamido or ureido;

R^8a is hydrogen or acetyl;

R⁵ is (Ci-C₄)-alkyl or -COOM; R⁶ is hydrogen, CN or -CONH₂;

L is 1 ,2-phenylene, 1 ,3-phenylene or 1 ,4 phenylene, which are unsubstituted or substituted by -SO₃M₁ -COOM or R⁸, or is (C₂-C₆)-alkylene or (Ci-C₄)-alkylene- phenylene which are unsubstituted or substituted by R⁸;

M is defined as given above; and * is the bond to the group RG. Examples of 5- or 6-membered heterocyclic residues comprising one or two heteroatoms standing for E¹ are pyridones, pyrazolones and diaminopyridines. Similarly, examples of divalent 5- or 6-membered heterocyclic residues comprising one or two heteroatoms standing for E² are divalent pyridone, pyrazolone and diaminopyridine residues.

Especially preferred aromatic or heteroaromatic divalent groups standing for X¹ correspond to the formulae (Him) to (NIu)

wherein * is the bond to the group RG and M is defined as given above. Preferred reactive groups capable of forming a covalent bond to carboxamido- and/or hydroxyl-containing material under dyeing conditions standing for RG are -SO₂-CH=CH₂, -SO₂-CH₂CH₂Z² or a group of the formula (IV)

-N(R⁸)-A (IV) wherein

Z² is an alkali-eliminatable group; R⁸ is defined as given above; A is a group of the formula (Va), (Vb) or (Vc)

V is fluorine or chlorine;

U¹and U² are independently fluorine, chlorine or hydrogen; and Q¹ and Q² are independently chlorine, fluorine, cyanamido, hydroxyl, (Ci-C₆)-alkoxy, phenoxy, sulfophenoxy, mercapto, (Ci-C₆)-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the formula (Vl) or (VII)

.R⁹ R¹⁰

-N, ₃ -N w-^so*^z (Vi) R¹¹ _{(VI I)} where

R⁹ has one of the meanings of R¹;

R¹⁰ and R¹¹ independently have one of the meanings of R¹ or combine to form a group of the formula -(CH₂)j- or of the formula -(CH₂)2-B¹-(CH₂)2-, where j is 4 or 5, B¹ is oxygen, sulfur, sulfonyl or -NR⁹- and R⁹ is (d-C₆)-alkyl;

W is phenylene which is unsubstituted or substituted by 1 or 2 substituents selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, carboxyl, sulfo, chlorine and bromine, or is (Ci-C₄)-alkylenephenylene, (C₂-C₆)-alkylene, which may be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl or carboxamido, or is phenylene CONH phenylene which is unsubstituted or substituted by 1 or 2 substituents selected from the group consisting of (CrC₄)-alkyl, (Ci-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido and halogen, or is naphthylene which is unsubstituted or substituted by one or two sulfo groups; and Z³ is -CH=CH₂ or -CH₂CH₂Z². Especially preferred reactive groups capable of forming a covalent bond to cellulose under dyeing conditions standing for RG are the groups of the formulae (Vd) to (Vi)

-SO₂-CH=CH₂ (Vd) -SO₂-CH₂CH₂OSO₃M (Ve)

wherein R⁸ and M are defined as given above.

In the formulae disclosed in this specification alkyl groups may be straight chain or branched and are in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec- butyl and tert-butyl. (Ci-C₆)-alkyl groups may in addition be n-pentyl or n-hexyl. Methyl and ethyl are preferred. The same logic applies to alkoxy groups, which accordingly are preferably methoxy and ethoxy and to alkylene groups, which are in particular ethylene, propylene and butylene. Halogen is preferably bromine, chlorine and fluorine. Alkali M is in particular lithium, sodium or potassium; an alkaline earth metal equivalent M is in particular the equivalent of calcium. M is preferably hydrogen or sodium.

Alkali-eliminatable groups standing for Z¹ or Z² are for example halogen, such as chlorine and bromine; ester groups of organic carboxylic and sulfonic acids, for example alkylcarboxylic acids, substituted or unsubstituted benzenecarboxylic acids and substituted or unsubstituted benzenesulfonic acids, in particular alkanoyloxy of 2 to 5 carbon atoms such as acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluylsulfonyloxy; also acidic ester groups of inorganic acids, as of phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato groups) and dialkylamino groups having alkyl groups of 1 to 4 carbon atoms each, such as dimethylamino and diethylamino. Z¹ is preferably chloro and more preferably sulfato. R² is preferably hydrogen, methyl or methoxy. M is preferably hydrogen, sodium or potassium.

Preferred dyestuffs of the formula (I) correspond to the formulae (Ia) and (Ib)

wherein X¹, Z¹ and RG are defined as given above. Especially preferrered are dyestuffs of the formulae (Ia) and (Ib) wherein Z¹ is -CH=CH₂ Or -CH₂CH₂OSO₃M¹, wherein M¹ is hydrogen or sodium.

Other especially preferred dyestuffs of the formula (I) correspond to the formulae (Ia) and (Ib), wherein X¹, RG and M have preferred meanings as defined above.

Accordingly, exceptionally preferred dyestuffs of the formula (I) are for example the dyestuffs of the formulae (Ic) to (Ij)

_(|d)

wherein A¹ is a group of the formula (Vf), (Vg), (Vh) or (Vi); A² is a group of the formula (Vd) or (Ve); R¹² is methyl, methoxy or -SO3M; and Z¹ and M are defined as given above.

The dyestuffs of the formula (I) can be prepared by synthesis steps which are known to a skilled person.

In a preferred method, a compound of the formula (Vl)

wherein R¹ , R², Z¹, a, b and M are defined is given above, is diazotized and coupled onto a compound of the formula (VII)

X¹-RG (VII) wherein X¹ and RG are defined as given above.

The compounds of formula (VII) are known and can be prepared by known methods.

The compounds of formula (Vl) are novel. Accordingly, the present invention also provides compounds of the formula (Via)

R¹ is F or CF₃;

Z¹ is -CH=CH₂ Or -CH₂CH₂G wherein G is hydoxy or a alkali-eliminatable group;

R² is hydrogen, (Ci-C₄)-alkyl, (C₁-C₄^aIkOXy, hydroxy or chlorine; a is 0, 1 or 2; b is 1 in case R¹ is CF₃ and is 1 or 2 in case R¹ is F; and M is hydrogen, an alkali metal or an equivalent of an alkaline earth metal.

Examples of preferred compounds of the formula (Via) are the compounds of formulae (VIaI) and (Vla2)

wherein Z¹ is -CH=CH₂ Or -CH₂CH₂OSOaM, with M being defined as given above.

The compounds of the formula (Via) wherein Z¹ is -CH₂CH₂OSO₃M can be prepared in line with the following multistep procedure starting from the compound of formula (VII)

The present invention's dyes of the formula (I) have useful application properties and can be used for dyeing and printing carboxamido- and/or hydroxyl-containing materials. The materials mentioned can be present for example in the form of sheetlike constructions such as paper and leather, in the form of films, as for example polyamide films, or in the form of a bulk composition, for example composed of polyamide or polyurethane. In particular, however, they are present in the form of fibres of the materials mentioned.

Thus, the present invention's dyes of the formula (I) are used for dyeing and printing cellulosic fibrous materials of any kind. They are preferably also useful for dyeing or printing polyamide fibres or of blend fabrics of polyamide with cotton or with polyester fibres.

It is also possible to use the present invention's dyes of the formula (I) to print textiles or paper by the ink jet process.

The present invention thus also provides for the use of the present invention's dyes of the formula (I) for dyeing or printing carboxamido- and/or hydroxyl-containing materials, or as the case may be for processes for dyeing or printing such materials in a conventional manner wherein one or more dyes of the formula (I) according to the present invention are utilized as a colorant.

Advantageously, the as-synthesized solutions of the present invention's dyes of the formula (I), if appropriate after addition of a buffer substance, and if appropriate also after concentrating or diluting, can be directly used for dyeing as a liquid preparation. Fibrous materials or fibres herein refer in particular to textile fibers which can be present as wovens, yarns or in the form of hanks or wound packages.

Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.

Hydroxyl-containing materials are those of natural or synthetic origin, for example cellulosic fibre materials or their regenerated products and polyvinyl alcohols.

Cellulosic fibre materials are preferably cotton, but also other vegetable fibres, such as linen, hemp, jute and ramie fibers. Regenerated fibres of cellulose are for example staple viscose and filament viscose.

The present invention's dyes of the formula (I) can be applied to and fixed on the materials mentioned, in particular on the fibrous materials mentioned, by the application techniques known for water-soluble dyes, in particular known for fibre- reactive dyes.

Wool which has been given a nonfelting or low-felting finish (cf. for example H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd edition (1972), pp. 295-299, in particular the finish by the so-called Hercosett process (p. 298); J. Soc. Dyers and Colourists 1972, 93-99, and 1975, 33-44) can be dyed with very good fastness properties. The process of dyeing on wool is here carried out in a conventional manner from an acidic medium. For instance, acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH. To obtain a dyeing of acceptable levelness, it is advisable to add a customary leveling agent, for example on the basis of a reaction product of cyanuric chloride with 3 times the molar amount of an aminobenzenesulfonic acid and/or of an aminonaphthalenesulfonic acid or on the basis of a reaction product of for example stearylamine with ethylene oxide. For instance, the dyes of the present invention are preferably subjected to the exhaust process initially from an acidic dyebath having a pH of about 3.5 to 5.5 under pH control and the pH is then, toward the end of the dyeing time, shifted into the neutral and optionally weakly alkaline range up to a pH of 8.5 to bring about, especially for very deep shades, the full reactive bond between the dyes of the present invention and the fibre. At the same time, the dye portion not reactively bound is removed.

The procedure described herein also applies to the production of dyeings on fibre materials composed of other natural polyamides or of synthetic polyamides and polyurethanes. These materials can be dyed using the customary dyeing and printing processes described in the literature and known to one skilled in the art (see for example H.-K. Rouette, Handbuch der Textilveredlung, Deutscher Fachverlag GmbH, Frankfurt/Main).

The dyeing liquors and print pastes, as well as the dyes of the formula (I) may contain further additions. Additions are for example wetting agents, antifoam agents, leveling agents and agents which influence the properties of the textile material, such as softeners, additions for a flameproof finish and soil-, water- and oil-rejecting or water-softening agents. Print pastes in particular may also contain natural or synthetic thickeners, such as for example alginates and cellulose ethers. The dye quantities in the dyebaths and print pastes can vary within wide limits according to the desired depth of shade. Generally, the dyes of the formula (I) are present in amounts of 0.01 % to 15% by weight and in particular in amounts of 0.1 % to 10% by weight based respectively on the material to be dyed and on the print paste.

On cellulose fibres they produce by the exhaust method from a long liquor using a wide variety of acid-binding agents and if appropriate neutral salts, such as sodium chloride or sodium sulfate, dyeings having very good color yields. Application of the dye is preferably at a pH of 3 to 7, and in particular at a pH of 4 to 6 for the exhausts method. The liquor ratio can be chosen within a wide range and is for example between 3:1 and 50:1 , preferably between 5:1 and 30:1. Dyeing is preferably carried out in an aqueous bath at temperatures between 40 and 105⁰C, if appropriate at a temperature of up to 13O⁰C under pressure, and if appropriate in the presence of customary dyeing auxiliaries. To increase the wetfastnesses of the dyed material, unfixed dye can be removed in an aftertreatment. This aftertreatment is carried out in particular at a pH of 8 to 9 and temperatures of 75 to 8O⁰C.

One possible procedure here is to introduce the material into the warm bath and to gradually heat the bath to the desired temperature and complete the dyeing process at that temperature. The neutral salts which accelerate the exhaustion of the dyes may also if desired only be added to the bath after the actual dyeing temperature has been reached.

Padding processes likewise provide excellent color yields and a very good color buildup on cellulose fibres, the dyes being fixable in a conventional manner by batching at room temperature or elevated temperature, for example at up to about 6O⁰C, by steaming or using dry heat.

Similarly, the customary printing processes for cellulose fibers, which can be carried out in one step, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and by subsequent steaming at 100 to 103⁰C, or in two steps, for example by printing with a neutral or weakly acidic print color and then fixing either by passing the printed material through a hot electrolyte- containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor and subsequent batching or steaming or dry heat treatment of the alkali-overpadded material, produce strong color prints with well-defined contours and a clear white ground. The outcome of the prints is affected by variations in the fixing conditions.

When fixing by means of dry heat in accordance with the customary thermofix processes, hot air at 120 to 200⁰C is used. In addition to the customary steam at 101 to 103⁰C, it is also possible to use superheated steam and high-pressure steam at temperatures of up to 16O⁰C.

The acid-binding agents which effect the fixation of the dyes on the cellulose fibers are for example water-soluble basic salts of alkali metals and likewise alkaline earth metals of inorganic or organic acids or compounds which liberate alkali in the heat. Especially suitable are the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being the sodium and potassium compounds. Such acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate, waterglass or trisodium phosphate.

The present invention's dyes of the formula (I) are notable for high reactivity, good fixing ability, very good build-up ability and also high light and perspiration light fastness. They can therefore be applied by the exhaust dyeing process at low dyeing temperatures and require only short steam times in the pad-steam process. The degrees of fixation are high and unfixed portions are readily washed off with the difference between the degree of exhaustion and the degree of fixation being remarkably small, i.e., the loss on soaping is very low. They are also particularly useful for printing, particularly on cotton, but also for printing nitrogenous fibers, for example wool or silk or blend fabrics containing wool or silk.

The present invention's dyes of the formula (I) are notable for unfixed portions of dye being readily washed off the fibrous material after the dyeing operation without whites included in the washing operation being stained or tainted by the dye which comes off. This results in advantages for the dyeing operation, in which washing cycles and hence costs are saved.

The dyeings and prints produced using the present invention's dyes of the formula (I) possess a high color strength and a high fibre-dye bond stability not only in the acidic region but also in the alkaline region, and also good light fastness and very good wet fastness properties, such as wash, water, seawater, cross-dyeing and perspiration fastnesses and also good fastness to pleating, hotpressing and crocking.

The present invention also provides inks for digital textile printing by the ink jet process, the inks comprising a present invention's dye of the formula (I). The present invention's inks contain one or more of the present invention's dyes of the formula (I), for example in amounts from 0.1% by weight to 50% by weight, preferably in amounts from 1% by weight to 30% by weight and more preferably in amounts from 1 % by weight to 15% by weight, based on the total weight of the ink. For the inks to be used in the continuous flow process, a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include for example lithium nitrate and potassium nitrate. The inks of the present invention may include organic solvents at a total level of 1-50% and preferably 5-30% by weight. Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1- propanol, isopropanol, 1-butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1 ,2-ethanediol, 1 ,2,3-propanetriol, butanediol, 1 ,3-butanediol, 1 ,4- butanediol, 1 ,2-propanediol, 2,3-propanediol, pentanediol, 1 ,4-pentanediol, 1 ,5- pentanediol, hexanediol, D,L-1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2,6-hexanetriol, 1 ,2- octanediol, polyalkylene glycols, for example: polyethylene glycol, polypropylene glycol, alkylene glycols having 2 to 8 alkylene groups, for example: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, low alkyl ethers of polyhydric alcohols, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether, polyalkylene glycol ethers, such as for example: polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines, such as for example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives, such as for example: urea, thiourea, N-methylurea, N,N'-epsilon dimethylurea, ethyleneurea, 1 ,1 ,3,3- tetramethylurea, N-acetylethanolamine, amides, such as for example: dimethylformamide, dimethylacetamide, acetamide, ketones or keto alcohols, such as for example: acetone, diacetone alcohol, cyclic ethers, such as for example: i tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma butyrolactone, epsilon-caprolactam, further sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide, N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, 1-(3-hydroxypropyl)-2-pyrrolidone, 1 ,3-dimethyl- 2-imidazolidinone, 1 ,3-dimethyl-2-imidazolinone, 1 ,3-bismethoxymethylimidazolidine, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol, pyridine, piperidine, butyrolactone, trimethylpropane, 1 ,2-dimethoxypropane, dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether, 1 ,2-dimethoxypropane and trimethylpropane. The inks of the invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in a temperature range from 20 to 50°C. Preferred inks have a viscosity of 1.5 to 20 mPas and particularly preferred inks have a viscosity of 1.5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane and nonionic cellulose ethers.

As further additives the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mN/m, which are adapted if necessary as a function of the process used (thermal or piezo technology). Useful surface-active substances include for example all surfactants, preferably nonionic surfactants, butyldiglycol and 1 ,2-hexanediol.

The inks may further include customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1% by weight based on the total weight of the ink. The inks of the invention may be prepared in a conventional manner by mixing the components in water.

The inks of the invention are particularly useful in inkjet printing processes for printing a wide variety of pretreated materials, such as silk, leather, wool, cellulosic fibre materials of any kind, polyurethanes and polyamide fibres. The printing inks of the invention are also suitable for printing pretreated hydroxyl-containing and/or amino- containing fibers present in blends, examples being blends of cotton, silk, wool with polyester fibres or polyamide fibres.

In contrast to conventional textile printing, where the printing ink already contains all the fixing chemicals and thickeners for a reactive dye, in inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step.

The pretreatment of the textile substrate, for example cellulose and regenerated cellulose fibres and also silk and wool, is effected with an aqueous alkaline liquor prior to printing. To fix reactive dyes there is a need for alkali, for example sodium carbonate, sodium bicarbonate, sodium acetate, trisodium phosphate, sodium silicate, sodium hydroxide, alkali donors such as, for example, sodium chloroacetate, sodium formate, hydrotropic substances such as, for example, urea, reduction inhibitors, for example sodium nitrobenzenesulfonates, and also thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannans.

These pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried.

After printing, the textile fiber material is dried at 120 to 150⁰C and subsequently fixed.

The fixing of the inkjet prints prepared with reactive dyes may be effected at room temperature or with saturated steam, with superheated steam, with hot air, with microwaves, with infrared radiation, with laser or electron beams or with other suitable energy transfer techniques.

A distinction is made between one- and two-phase fixing processes. In one-phase fixing, the necessary fixing chemicals are already on the textile substrate. In two- phase fixing, this pretreatment is unnecessary. Fixing only requires alkali, which, following inkjet printing, is applied prior to the fixing process, without intermediate drying. There is no need for further additives such as urea or thickener.

Fixing is followed by the print aftertreatment, which is the prerequisite for good fastnesses, high brilliance and an impeccable white ground.

The prints produced with the inks of the present invention possess high color strength and a high fiber-dye bond stability not only in the acidic but also in the alkaline region, also good lightfastness and very good wet fastness properties such as fastness to washing, water, seawater, crossdyeing and perspiration, and also good fastness to pleating, hotpressing and crocking.

The compounds described in the examples in terms of a formula are indicated in the form of their free acid, even though they are generally prepared and isolated in the form of their salts, preferably sodium or potassium salts, and used for dyeing in the form of their salts.AII λmax values for the examples below have been measured in water.

Example 1 Preparation of Sulfuric acid mono-[2-(4-amino-2-trifluoromethyl-benzenesulfonyl)- ethyl] ester

a) Preparation of 2-(4-Nitro-2-trifluoromethyl-phenylsulfanyl)-ethanol

In a 3-neck 250ml round bottom flask fitted with an overhead stirrer, thermometer and a drying tube was charged potassium carbonate (18.5g), dimethyl sulphoxide

(10OmIs) and 2-fluoro-5-nitrobenzotrifluoride (41.82g).

To this yellow suspension was added 2-mercaptoethanol (15.79g) drop wise over

45mins allowing the temperature to exotherm to 43⁰C and then cool back to ambient temperature. The reaction mixture was drowned-out into 2N hydrochloric acid (400ml), an oil separated and was allowed to settle before collecting. (53.45g). The oil was used in the next step without purification.

The oil exhibited analytical data consistent with the expected structure.

b) Preparation of 2-(4-Nitro-2-trifluoromethyl-benzenesulfonyl)-ethanol In a 3-neck 250ml round bottom flask fitted with an overhead stirrer, condenser, thermometer and a dropping funnel was charged 2-(4-Nitro-2-trifluoromethyl- phenylsulfanyl)-ethanol (53.45g) and water (100ml). Sodium tungstate dihydrate (0.66g) was added and the reaction mixture heated to 7O⁰C at which time hydrogen peroxide (30% w/v 74mls) was added dropwise over 20min. whilst allowing the reaction to exotherm to reflux. The mixture was heated at reflux for a further 4Hrs before allowing to cool to room temperature overnight.

A solid precipitated and was collected by filtration, pulled dry to afford the sulphone product (59.85g) which was used in the next stage without purification. The solid exhibited analytical data consistent with the expected structure.

c) Preparation of 2-(4-Amino-2-trifluoromethyl-benzenesulfonyl)-ethanol

In a 4-neck 2000ml round bottom flask fitted with an overhead stirrer, condenser, thermometer and a stopper was charged methylated spirits (200ml) and iron powder (114g). 2N hydrochloric acid (75ml) was added and stirred for 2mins. 2-(4-Nitro-2- trifluoromethyl-benzenesulfonyl)-ethanol (59.85g) was dissolved in methylated spirits (1000ml) and added in one portion to the reaction mixture. The mixture was then stirred and heated to reflux for 2hrs. The reaction was cooled to room temperature and basified with 2N sodium hydroxide (50ml) to pH8.0-8.5 before filtering off and discarding the solid. The filtrate was acidified with cone, hydrochloric acid (10ml) and concentrated in vacuo to dryness to afford an orange viscous oil (53.85g) which was used in the next stage without purification. The oil exhibited analytical data consistent with the expected structure.

d) Preparation of Sulfuric acid mono-[2-(4-amino-2-trifluoromethyl-benzenesulfonyl)- ethyl] ester

In a 3-neck 500ml round bottom flask fitted with an overhead stirrer, condenser, thermometer and a stopper was charged sulphuric acid (240ml; 98%). Oleum (30ml; 65%) was added dropwise over 20mins whilst maintaining internal temperature <20°C. The 2-(4-Amino-2-trifluoromethyl-benzenesulfonyl)-ethanol (53.85g) was added portionwise over 20mins maintaining the internal temperature at<20°C. The reaction mixture was stirred overnight before drowning out onto ice (35Og) with vigorous stirring. The resultant solid was collected by filtration and pulled dry. The wet-cake was slurried with acetonitrile (200ml) filtered and pulled dry to yield a white powder (56.54g) which exhibited analytical data consistent with the expected structure.

Example 2

Preparation of sulfuric acid mono-[2-(4-amino-2-fluoro-benzenesulfonyl)-ethyl] ester

a)Preparation of 2-(2-Fluoro-4-nitrophenylsulfanyl)-ethanoI

In a 3-neck 100ml round bottom flask fitted with an overhead stirrer, thermometer and a drying tube was charged potassium carbonate (11.61 g), dimethyl sulphoxide

(5OmIs) and 3,4-difluoronitroaniline (20.04g).To this yellow suspension was added 2- mercaptoethanol (12.39g) dropwise allowing the mixture to exotherm to reach 4O⁰C before cooling back to ambient temperature.

The orange reaction mixture was drowned-out into 2N hydrochloric acid (200ml), initially an oil separated before it solidified to a bright yellow solid. The yellow solid was collected by filtration and pulled dry (26.28g) and was used in the next step without purification. The solid exhibited analytical data consistent with the expected structure.

b) Preparation of 2-(2-Fluoro-4-nitro-benzenesulfonyl)-ethanol

In a 3-neck 250ml round bottom flask fitted with an overhead stirrer, condenser, thermometer and a dropping funnel was charged 2-(2-Fluoro-4- nitrophenylsulfanyl)ethanol (26.28g) and water (100ml). Sodium tungstate dihydrate (0.4g) was added and the reaction mixture heated to 7O⁰C at which time hydrogen peroxide (3OmIs, 30% w/v) was added dropwise over IOmins whilst allowing the reaction to exotherm to reflux. The reaction mixture (yellow solution) was heated at reflux for a further 1Hr before allowing to to room temperature. A solid precipitated and was collected by filtration, pulled dry to afford 25.35g of product which was used in the next stage without purification. The solid exhibited analytical data consistent with the expected structure.

c) Preparation of 2-(4-Amino-2-fluoro-benzenesulfonyl)-ethanol In a 4-neck 1000ml round bottom flask fitted with an overhead stirrer, condenser, thermometer and a stopper was charged methylated spirits (100ml) and iron powder (58.1g). 2N hydrochloric acid (50ml) added and stirred for 2mins. To this strirred mixture was added 2-(2-Fluoro-4-nitro-benzenesulfonyl)-ethanol (25.35g) dissolved in methylated spirits (800ml) before heating at reflux for 30mins and allowing to cool to room temperature. The reaction mixture was basified with 10% sodium carbonate (90ml) to pH8.0-8.5 and filtered, solid discarded and the filtrate concentrated in vacuo to dryness. The residue an off-white solid was collected and dried at 4O⁰C and was used in the next stage without purification. The solid exhibited analytical data consistent with the expected structure.

d) Preparation of sulfuric acid mono-[2-(4-amino-2-fluoro-benzenesulfonyl)-ethyl] ester

In a 3-neck 250ml round bottom flask fitted with an overhead stirrer, condenser, thermometer and a stopper was charged sulphuric acid (120ml; 98%) and oleum (15ml; 65%) was added dropwise over 20mins, whilst maintaining internal temperature <20°C. To this mixture was added all of the 2-(4-Amino-2-fluoro- benzenesulfonyl)-ethanol from the previous preparation portionwise over 20mins, with the internal temperature maintained at<20°C. After the addition the reaction mixture was stirred overnight at room temperature. The reaction mixture (straw coloured solution) was drowned out onto crushed ice (20Og) with vigorous stirring. The resultant solid was collected by filtration and pulled dry. The wet-cake was slurried with acetone (75ml) filtered and pulled dry to yield a white solid (24.51 g) which exhibited analytical data consistent with the expected structure.

Example 3 Sulfuric acid mono-[2-(4-amino-2-trifluoromethyl-benzenesulfonyl)-ethyl] ester

(2.86 g, 0.0082 mol) was added to water (5OmIs) with stirring and the pH adjusted to 6.5 with 10% sodium bicarbonate solution to effect solution. Sodium nitrite (0.57g, 0.0082mol) was added to the solution and after IOmins stirring the solution was added dropwise to a stirred mixure of ice (5Og) and cone. HCI (1 OmIs) ensuring the temperature remained <5°C by the use of external cooling. After a further 30mins the diazotization was complete and the excess nitrite was destroyed by the addition of sulphamic acid. The monoazo dye of the formula

(7.08g, 0.0082mol) prepared according to the art was dissolved in water (10OmIs) before adding the solution of the diazonium salt portionwise over 15mins maintaining the pH at 5.0-6.0 throughtout via the addition of 2N sodium carbonate solution. After stirring over night the reaction mixture was evaporated to lower volume and methylated spirits added to precipitate the expected product as a dark solid (10.55g) which exhibited analytical data consistent with the expected structure of formula (If1 )

λmax 595nm

The dyestuffs according to the following Examples 4 to 17 can be obtained according to the methods described in Example 3

Example 20

A textile fabric consisting of mercerized cotton is padded with a liquor containing

35 g/l of anhydrous sodium carbonate, 100 g/l of urea and 150 g/l of a low viscosity sodium alginate solution (6%) and then dried. The wet pick-up is 70%.

The textile thus pretreated is printed with an aqueous ink containing 2% of the dye obtained according to Example 1 , 20% of sulfolane, 0.01% of Mergal K9N and

77.99% of water using a drop-on-demand (bubble jet) ink jet print head. The print is fully dried. Fixation is effected by means of saturated steam at 102⁰C for 8 minutes.

The print is subsequently rinsed warm, subjected to a fastness wash with hot water at 95°C, rinsed warm and then dried to obtain a print having excellent service fastnesses.

Claims

Patent Claims

1. Dyestuff of the formula (I)

wherein

R¹ is F or CF₃;

Z¹ is -CH=CH₂ Or -CH₂CH₂G wherein G is a alkali-eliminatable group;

R² is hydrogen, (Ci-C₄)-alkyl, (C-ι-C₄)-alkoxy, hydroxy or chlorine;

X¹ is an aromatic or heteroaromatic divalent group; RG is a reactive group capable of forming a covalent bond to carboxamido- and/or hydroxyl-containing material under dyeing conditions or a group comprising a reactive group capable of forming a covalent bond to cellulose under dyeing conditions or is hydrogen; a is O₁ 1 or 2; b is 1 in case R¹ is CF₃ and is 1 or 2 in case R¹ is F; and

M is hydrogen, an alkali metal or an equivalent of an alkaline earth metal.

2. Dyestuff according to claim 1 , wherein X¹ corresponds to one of the formulae (Ilia) to (I I Ik)

(NIC) (MId) (MIe)

wherein

Ar is phenylen or phenylen which is substituted by 1 , 2 or 3 substituents selected from the group comprising (CrC₄)-alkyl, (Ci-C₄)-alkoxy, hydroxy, trifluormethyl, chlorine, fluorine and -SO₃M;

E¹ has one of the meanings of Ar , is naphthyl or naphthyl which is substituted by 1 , 2 or 3 substituents selected form the group comprising (CrC₄)-alkyl, (Ci-C₄)-alkoxy, - SO₃M, amino, acetylamino or hydroxy; or is a 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, or is a 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, which is substituted by 1 , 2 or 3 substituents selected from the group comprising (Ci-C₄)-alkyl and (Ci-C₄)-alkoxy;

E² is phenylene or naphthylene which are unsubstituted or substituted by 1 , 2 or 3 substituents selected from the group comprising (CrC₄)-alkyl, (Ci-C₄)-alkoxy -SO₃M, amino, acetylamino or hydroxy; or is a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, or is a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, which is substituted by 1 , 2 or 3 substituents selected from the group comprising (C-ι-C₄)-alkyl and (Ci-C₄)-alkoxy; or is a group of the formula (IV)

wherein R⁷ is (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy -SO₃M or hydroxy; R⁸ and R⁸' independently are hydrogen, (d-C₆)-alkyl, sulfo-(Ci-C₆)-alkyl, phenyl or phenyl substituted by (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, hydroxyl, -SO₃M, halogen, - COOM, acetamido or ureido; R^8a is hydrogen or acetamido; R⁵ is (C_rC₄)-alkyl or -COOM; R⁶ is hydrogen, CN or -CONH₂;

L is 1 ,2-phenylene, 1 ,3-phenylene or 1 ,4 phenylene, which are unsubstituted or substituted by -SO₃M, -COOM or R⁸, or is (C₂-C₆)-alkylene or (Ci-C₄)-alkylene- phenylene which are unsubstituted or substituted by R⁸; M is defined as given above; and * is the bond to the group RG.

3. Dyestuff according to claim 1 and/or 2, wherein RG is -Sθ₂-CH=CH₂, -SO₂-CH₂CH₂Z¹ or a group of the formula (IV) -N(R⁸)-A (IV) wherein

Z¹ is an alkali-eliminatable group; R⁸ is defined as given above; A is a group of the formula (Va), (Vb) or (Vc)

V is fluorine or chlorine;

U¹and U² are independently fluorine, chlorine or hydrogen; and Q¹ and Q² are independently chlorine, fluorine, cyanamido, hydroxyl, (C-ι-C₆)-alkoxy, phenoxy, sulfophenoxy, mercapto, (d-Ce^alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the formula (Vl) or (VII)

R⁹

,R¹⁰

— N — N

W-SO₂Z²

(Vl) V¹ (VIl) where

R⁹ has one of the meanings of R¹; R¹⁰ and R¹¹ independently have one of the meanings of R¹ or combine to form a group of the formula -(CH₂)j- or of the formula -(CH₂)₂-B¹-(CH₂)2-_> where j is 4 or 5, B¹ is oxygen, sulfur, sulfonyl or -NR⁹- and R⁹ is (Ci-C₆)-alkyl;

W is phenylene which is unsubstituted or substituted by 1 or 2 substituents selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, carboxyl, sulfo, chlorine and bromine, or is (Ci-C₄)-alkylenephenylene, (C₂-C₆)-alkylene, which may be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl or carboxamido, or is phenylene CONH phenylene which is unsubstituted or substituted by 1 or 2 substituents selected from the group consisting of (Ci-C₄)-alkyl, (CrC₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido and halogen, or is naphthylene which is unsubstituted or substituted by one or two sulfo groups; and Z² is -CH=CH₂ or -CH₂CH₂Z¹.

4. Dyestuff according to one or more of claims 1 to 3, which corresponds to one of the formulae (Ia) and (Ib)

wherein X I ^ ₁ Z -7I and RG are defined as given in claim 1.

5. Dyestuff according to one or more of claims 1 to 4, which corresponds to one of formulae (Ic) to (Ij)

wherein

A¹ is a group of the formula (Vf), (Vg), (Vh) or (Vi) N N

N_κ ^N

,N,

H (Vf) (Vg)

wherein R⁸ is defined as given in claim 2 and M is defined as given in claim 1 ;

A is a group of the formula (Vd) or (Ve)

-SO₂-CH=CH₂ (Vd) -SO₂-CH₂CH₂OSO₃M (Ve) wherein M is defined as given in claimi ; R¹² is methyl, methoxy or -SO₃M; and Z¹ and M are defined as given above.

6. Method for the preparation of a dyestuff of formula (I) according to claim 1 , wherein a compound of the formula (Vl)

wherein R¹, R², Z¹, a, b and M are defined is given above, is diazotized and coupled onto a compound of the formula (VII)

X¹-RG (VII) wherein X¹ and RG are defined as given in claim 1.

7. The use of a dye of the formula (I) according to claim 1 for dyeing or printing carboxamido- and/or hydroxyl-containing materials.

8. An ink for digital textile printing by the ink jet process, comprising a dye of the formula (I) according to claim 1.

9. Compound of the formula formula (Via)

R¹ is F Or CF₃; Z¹ is -CH=CH₂ Or -CH₂CH₂G wherein G is hydoxy or a alkali-eliminatable group;

R² is hydrogen, (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, hydroxy or chlorine; a is O, 1 or 2; b is 1 in case R¹ is CF₃ and is 1 or 2 in case R¹ is F; and

M is hydrogen, an alkali metal or an equivalent of an alkaline earth metal.

10. Compound according to claim 9, which corresponds to one of the formulae (VIaI) and (Vla2)

wherein Z¹ is -CH=CH₂ or -CH₂CH₂OSO₃M, with M being defined as given in claim 9.