Disperse dye mixtures

This application is a national stage application (under 35 U.S.C. 371) of PCT/EP2005/055028 filed Oct. 5, 2005, which claims benefit of United Kingdom application 0422403.6 filed Oct. 8, 2004.

This invention relates to mixtures of dull blue to navy disperse dyes, particularly a mixture of disperse polycyclic dyes with other disperse azo, anthraquinone or benzodifuranone dyes to achieve deep black shades and to a process for the coloration of synthetic textile materials and to textile materials when coloured with the mixture of dyes.

Mixed disperse dyes and their use for dyeing polyester and its blends with other fibres such as cellulose, polyurethane, nylon and wool by normal exhaust dyeing, continuous dyeing and direct printing techniques are already known for example from the document WO 9704031 or EP 0 492 893. However, they have certain application defects, such as for example relatively poor leveling/migration properties, an overly large dependence of the colour yield on varying dyeing parameters in the dyeing process or an insufficient colour build-up on polyester (good colour build-up results from the ability of a dye to provide a proportionally stronger dyeing when used in higher concentrations in the dye bath), or unsatisfactory fastness properties.

Thus there is a need for disperse dyes which provide dyeings of improved colour build-up and fastness properties, i.e. wash and light fastness properties of dyed polyester or its blends with other fibres such as cellulose, polyurethane, nylon and wool.

The present invention, then, provides dye mixtures of disperse dyes which provide dyeings of very good colour build up, wet and light fastness properties on polyester or its blends with other fibres particularly in the deep black shade area.

The invention accordingly provides dye mixtures comprising one or more dyes of the herein below indicated and defined formula (I)

where

R 1 and R 2 are independently hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, aryl or aralkyl, or R 1 and R 2 together with the N atom can form a heterocyclic 5, 6 or 7 membered ring, R 3 and R 4 are independently hydrogen, halogen, or an optionally substituted alkyl, alkenyl or alkoxy or R 1 and R 3 together with the N atom can form a heterocyclic 5, 6 or 7 membered ring, R 2 and R 4 together with the N atom can form a heterocyclic 5, 6 or 7 membered ring, R 5 is hydrogen, halogen or optionally substituted alkyl or alkoxy group or is —NR 01 R 02

where R 01 and R 02 independently have a meaning of R 1 and R 2

R 6 and R 7 are independently hydrogen, halogen, or an optionally substituted alkyl, alkenyl or alkoxy, R 5 and R 6 together with the N atom can form a heterocyclic 5, 6 or 7 membered ring, or R 5 and R 7 together with the N atom can form a heterocyclic 5, 6 or 7 membered ring and at least one dye of the herein below indicated and defined general dyes of:

formula (II),

or one or more dyes of general formula (III),

wherein

R 8 and R 9 are independently H, C 1 -C 4 alkoxy, C 1 -C 4 alkenyloxy [OR 10 ] optionally substituted by unsubstituted or substituted saturated or unsaturated 5-, 6-, or 7-membered heterocyclic or homocyclic residues or substituted alkoxy [O(CH 2 ) n R 11 }where

n can be an integer from 1 to 6 and R 11 can be OR 12 or COR 13

where R 12 is H, alkyl, alkenyl, aryl, alkoxyalkyl, aryloxyalkyl, carbonylalkyl, carbonylalkenyl, carbonylaryl, carbonylalkoxyalkyl or carbonylaryloxyalkyl, and R 13 is alkoxy, alkenyloxy, aryloxy, arylalkoxy, aryloxyalkoxy, alkenyloxyalkoxy or alkoxyalkoxy

or one or more dyes of general formula (IV),

wherein P and Q are independently O or NH and where at least one and preferably both P and Q are O.

n is an integer from 1 to 4, preferably 2 or 3, R 14 is H or C 1 -C 4 alkyl or a C 1 -C 4 alkoxy group

or alternatively, at least one of the herein below indicated and defined general dye of formula (IVa), (IVb) or (IVc).

whereas the preferred ratio of these two components would be 40-50 to 50-60 and especially preferred would be 45 to 55 parts,

wherein R is H or CH 3 . The preferred ratio of H to CH 3 would 30-70 to 70-30 and more preferred would be 40-60 to 60-40,

one or more dyes of general formula (V)

wherein

T, U and V are independently hydrogen, formyl, acetyl, chloro, bromo, cyano or nitro n=1-4 R 15 and R 16 are independently C 1 to C 4 alkyl, alkenyl, aryl, aralkyl, carbonylalkyl, carbonylalkenyl, carbonylaryl, carbonylalkoxyalkyl or carbonylaryloxyalkyl. R 17 is hydrogen, halogen, C 1 to C 4 alkyl or C 1 to C 4 alkoxy, NHCOR 18 ,

where R 18 is C 1 to C 4 alkyl or C 1 to C 4 alkoxy, where in case where R 17 is NHCOR 18 then (CH 2 ) n OR 15 /R 16 are replaced by R 19 and R 20 as given in structure (Va)

wherein

R 19 and R 20 are independently hydrogen, alkyl, alkenyl, aryl, aralkyl, alkoxyalkyl, aryloxyalkyl, alkoxycarbonylalkyl and alkylcarbonylalkoxy.

or one or more dyes of general formula (VI)

wherein

R 21 is H, alkyl, alkoxyalkyl or aryloxyalkyl, X is H, halogen, alkyl, nitro or cyano. Y is independently H, halogen, alkyl, nitro, alkoxyalkoxyakylcarbonyl, arylalkoxycarbonyl, mono or dialkylaminocarbonyl, or alkylalkoxycarbonyl in which the alkali group can be further substituted by a 5, 6 or 7 membered (saturated or unsaturated) heterocyclic ring, or Y is

R 22 SO 2

wherein R 22 is aryloxy, or mono/dialkylamino

Z is independently H, hydroxyl, halogen, or R 22 SO 2 wherein R 22 is aryloxy, or mono/dialkylamino or Z is aryloxyalkoxycarbonyl, or arylalkoxycarbonyl.

Preferred structures covered by the general formula (I) are for example as given in Table 1

Preferred structures covered by the general formula (III) are given in table 2

Preferred structures covered by the general formula (IV) are given in table 3

Preferred structures covered by the general formula (V) are given in table 4

In case where R 17 is NHCOR 18 then (CH 2 ) n OR 15 /R 16 are replaced by R 19 and R 20 as given in structure (Va)

wherein

R 19 and R 20 are independently hydrogen, alkyl, alkenyl, aryl, aralkyl, alkoxyalkyl, aryloxyalkyl, alkoxycarbonylalkyl and alkylcarbonylalkoxy as given in table 5:

Preferred structures covered by the general formula (VI) are given in table 6

The dyes according to the general formula (I) are known from EP 363 034 A2, mixtures of benzodifuranone dyes are known from WO 9704031.

Preferred mixtures according to the invention are two component mixtures comprising at least one dyestuff of general formula (I) and at least one dyestuff of formula (II), or at least one dyestuff of formula (IV), or at least one dyestuff of formula (V), or at least one dyestuff of formula (VI).

Especially preferred mixtures according to the invention comprise at least one dyestuff of general formula (I), one dyestuff of formula (II) and at least one dyestuff if general formula (VI).

Especially preferred are also mixtures comprising at least one dyestuff of general formula (I), dyestuff of formula (II), at least one dyestuff of general formula (IV) and at least one dyestuff of general formula (VI), as well as mixtures according to the invention comprising at least one dyestuff of general formula (I), dyestuff (II), at least one dyestuff of general formula (V) and at least one dyestuff of the general formula (VI), or inventive mixtures comprising at least one dyestuff of the general formula (I), at least one dyestuff of the general formula (III), at least one dyestuff of the general formula (IV) and at least on dyestuff of the general formula (VI).

Furthermore are especially preferred mixtures comprising one or more dyestuffs according to the general formula (I), one or more dyestuffs of the general formula (III), one or more dyestuffs of the general formula (V) and one or more dyestuffs according to the general formula (VI), as well as mixtures according to the invention comprising one or more dyestuffs according to the general formula (I), dyestuff (II), one or more dyestuffs according to the general formula (III), one or more dyestuffs according to the general formula (V) and one or more dyestuffs according to the general formula (VI), and dyestuff mixtures comprising one or more dyestuffs according to the general formula (I), dyestuff (II), one or more dyestuffs according to the general formula (III), one or more dyestuffs according to the general formula (IV), and one or more dyestuffs of the general formula (VI), and dyestuff mixtures comprising at least one dyestuff of the general formula (I), dyestuff (II), at least one dyestuff of the general formula (III), at least one dyestuff of the general formula (IV), at least one dyestuff of the general formula (V) and at least one dyestuff of the general formula (VI).

The preferred percentage of dye (I) in the final black mixture component or a would be 15% to 50% by weight and especially preferred would be 25% to 40% by weight.

The preferred percentage of dye (II) in the final black mixture would be 0% to 50% by weight, or 0 to 45% by weight and especially preferred would be 20% to 50% by weight.

The preferred percentage of dye (III) in the final black mixture either as the single component or a two/three component mixture would be 0% to 30% by weight and especially preferred would be 0% to 20% by weight.

The preferred percentage of dye (IV) in the final black mixture would be 0% to 40% by weight and especially preferred would be 0% to 25% by weight.

The preferred percentage of dye (V) in the final black mixture would be 0% to 30% by weight and especially preferred would be 0% to 20% by weight.

The preferred percentage of dye (VI) in the final black mixture would be 0 to 30% by weight, preferably 5% to 30% by weight and especially preferred would be 15% to 25% by weight.

Further examples of inventive mixtures are given in table 8. Ratios are given as % by weight.

If Dye (I) in Table 8 is a two component mixture as represented for example by structures I-1 and I-2 then the preferred ratios are 40:60 to 60:40 of I-1 to I-2 and more especially preferred would be a 50:50 ratio of I-1 to I-2. For a three component mixture as represented for example by I-1 and I-2 and I-3 then the preferred ratios would be 40:40:20 of I-1 to I-2 to I-3 and more especially preferred would be a 45:45:10 ratio of I-1 to I-2 to I-3.

If Dye (III) in Table 8 is a two component mixture as represented for example by structures III-1 and III-2 then the preferred ratios are 20:80 to 80:20 for III-1 to III-2 and more especially preferred ratios would be 40:60 to 60:40 of III-1 to III-2. For a three component mixture as represented for example by III-1 and III-2 and III-3 then the preferred ratio would be 5%-30% of III-1 to 35%-75% of III-2 and 20%-40% of III-3 and more especially preferred ratios would be 10%-20% of III-1 to 45%-65% of III-2 and 25%-35% of III-3.

If dye (IV) in Table 8 is a two component mixture as represented for example by structures IV-1 and IV-3 then the preferred ratios are 40:60 to 60:40 of IV-1 to IV-3 and more especially preferred would be a 50:50 ratio of IV-1 to IV-3. If dye (IV) is a two component mixture as represented by structures IVb then the preferred ratios are 40-60 and more especially preferred would be 45-55 ratio of the structures represented by IVb. For IVc the preferred ratio of H to CH 3 is 30-70 to 70-30 and much preferred would be 40-60 to 60-40.

Mixtures embodying the invention can be prepared, for example, by mixing the dye components in the required amounts. Suitable mixing methods include

Co-crystallisation

Typically, the dyes are dissolved in a hot solvent, for example, by placing the dyes in a suitable solvent and heating up to the reflux temperature of the solvent until the dyes are dissolved, thereafter filtering to provide a solution, and then allowing the solution to cool and crystals to form. The resultant mixture may then undergo further processing, such as milling and spray drying. Examples of suitable solvents for this process are organic solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, amides, sulphoxides, esters, ketones and ethers. Specific examples of organic solvents are toluene, ethyl cellosolve, acetone, chlorobenzene, pyridine, dimethyl formamide, dimethylsulphoxide, ethyl acetate, benzene, tetrahydrofuran and cyclohexane. Co-crystallisation is generally unsuitable for mixtures containing more than two components.

Co-milling

The dyes are mixed and then milled together to give an intimate blend which is then spray dried to give a solid mixture; or

Co-drying

Each dye is milled separately and then mixed in the required ratio before spray drying.

Dry-Blending

Each dye is spray dried separately and then mixed in the required ratio by a dry blending process.

Mixtures embodying the invention provide especially useful disperse dyes valuable for colouring synthetic textile materials and fibre blends thereof by exhaust dyeing, padding or printing, and may be formed into dispersions for this purpose. They may also be used in, for example, ink jet printing of textiles and non-textiles, dye diffusion, thermal transfer printing and in the colouration of plastics.

A particular aspect of the invention provides a composition comprising a mixture of dyestuffs of the general formula (I) with dyestuffs of the specific formula (III), and dyestuffs of general formula (IV) and (VI) and optionally dyestuffs of the general formula (III) and general formula (V), and additionally, at least one further ingredient conventionally used in colouring applications such as a dispersing agent and optionally a surfactant or wetting agent. The composition typically comprises from 1% to 65%, preferably 10 to 60%, more preferably 20 to 55%, of the total dye mixture in a solid medium.

Typical examples of dispersing agent are lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates and phenol/cresol/sulphanilic acid/formaldehyde condensates, typical examples of wetting agent are alkyl aryl ethoxylates which may be sulphonated or phosphated and typical example of other ingredients which may be present are inorganic salts, de-foamers such as mineral oil or nonanol, organic liquids and buffers. Dispersing agents may be present at from 10% to 200% on the weight of the dye mixtures. Wetting agents may be used at from 0% to 20% on the weight of the dye mixtures.

The compositions may be prepared by bead milling the dye mixture with glass beads or sand in an aqueous medium. The compositions may have further additions of dispersing agents, fillers and other surfactants and may be dried, by a technique such as spray drying, to give a solid composition comprising from 5% to 65% of dyestuff.

The resultant mixtures, are used to colour polyester (especially microfibre) and its blends with cellulose, elastane, nylon (conjugate microfibre) and wool in deep black shades with excellent levels of wet fastness

According to another aspect, the invention provides a process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material or fibre blend the dyestuff mixture according to the invention.

The synthetic textile material may be selected from aromatic polyester, especially polyethylene terephthalate and microfibre constructions thereof (including both sea island and conjugate microfibres, polyamide, especially polyhexamethylene adipamide, secondary cellulose acetate, cellulose triacetate, polyurethanes and natural textile materials, especially cellulosic materials and wool. An especially preferred textile material is an aromatic polyester or fibre blend thereof with fibres of any of the above mentioned textile materials. Especially preferred fibre blends include those of polyester-cellulose, such as polyester-cotton, polyester-wool, polyester/polyurethane and polyester/polyamide in the form of a conjugate microfibre. The textile materials or blends thereof may be in the form of filaments, loose fibres, yarn or woven or knitted fabrics.

The inventive dyestuff mixtures may be applied to the synthetic textile materials or fibre blends by processes which are conventionally employed in applying disperse dyes to such materials and fibre blends.

Suitable process conditions may be selected from the following

(i) exhaust dyeing at a pH of from 4 to 6.5, at a temperature of from 125° C. to 140° C. for from 10 to 120 minutes and under a pressure of from 1 to 2 bar, a sequestrant optionally being added; (ii) continuous dyeing at a pH of from 4 to 6.5, at a temperature of from 190° C. to 225° C. for from 15 seconds to 5 minutes, a migration inhibitor optionally being added; (iii) direct printing at a pH of from 4 to 6.5, at a temperature of from 160° C. to 185° C. for from 4 to 15 minutes for high temperature steaming, or at a temperature of from 190° C. to 225° C. for from 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 120° C. to 140° C. and 1 to 2 bar for from 10 to 45 minutes for pressure steaming, wetting agents and thickeners (such as alginates) of from 5 to 100% by weight of the dye optionally being added; (iv) discharge printing (by padding the dye on to the textile material, drying and overprinting) at a pH of from 4 to 6.5, migration inhibitors and thickeners optionally being added; (v) carrier dyeing at a pH of from 4 to 6.5, at a temperature of from 95° C. to 100° C. using a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol, sequestrants optionally being added; and (vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of 85° C. for acetate or at a temperature of 90° C. for triacetate and nylon for from 15 to 90 minutes, sequestrants optionally being added

In all the above processes, the dye mixture is applied as a dispersion comprising from 0.001% to 20%, preferably from 0.005 to 16%, of the dye mixture in an aqueous medium.

In addition to the above-mentioned application processes, the dye mixtures may be applied to synthetic textile materials and fibre blends by ink-jet printing. For ink-jet applications, the application medium may comprise water, dispersing agents, biocides, and a water-soluble organic solvent, preferably in a weight ratio of 1:99 to 99:1, more preferably 1:95 to 50:50 and especially in the range 10:90 to 40:60. The water-soluble organic solvent preferably comprises a C 1-4 -alkanol, especially methanol or ethanol, a ketone, especially acetone or methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone, a glycol, especially ethylene glycol, propylene glycol, trimethylene glycol, butane-2,3-diol, thiodiglycol or diethylene glycol, a glycol ether, especially ethylene glycol monomethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether, urea, a sulphone, especially bis-(2-hydroxyethyl) sulphone or mixtures thereof.

In contrast to conventional textile printing, in inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step. The pretreatment of the textile substrate is effected with thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannanes.

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, contact less 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 150° C. 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.

The dye mixtures may also be applied to textile materials using supercritical carbon dioxide, in which case the dye formulating agents may optionally be omitted.

Embodiments of the present invention will now be described in more detail with reference to the following examples, in which parts are by weight unless otherwise stated.