EP2035508A2

EP2035508A2 - Dye mixtures and their use for printing fibrous materials

Info

Publication number: EP2035508A2
Application number: EP07765426A
Authority: EP
Inventors: Markus Dorer; Helmut Niederschuh
Original assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Current assignee: Dystar Colours Distribution GmbH
Priority date: 2006-06-20
Filing date: 2007-06-14
Publication date: 2009-03-18
Also published as: WO2007147773A3; DE102006028262A1; TW200817480A; WO2007147773A2

Abstract

The invention relates to a dye mixture containing a dye of general formula (I) and at least one dye of general formula (II), in which the variables are defined as cited in claim 1. The invention also relates to a method for producing said mixtures and to the use thereof.

Description

Dye mixtures and their use for printing fiber materials

The invention is in the technical field of fiber-reactive azo dyes.

Commercially available dyes for printing hydroxyl-containing materials with reactive dyes (reactive printing) have certain application defects, such as a non-uniform, fiber-dependent color structure, especially in deep tones.

Surprisingly, it has now been found that yellow dye mixtures containing at least one vinylsulfongruppenhaltigen reactive dye of specific structure and at least one monochlorotriazine dye of certain structure, can solve this problem and in particular to remedy the shortcomings of the individual dyes.

The present invention thus relates to a dye mixture which comprises at least one dye of the general formula (I)

and at least one dye of the general formula (II)

wherein R ¹ and R ² independently of one another represent hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, sulfo, chlorine or bromine; R ³ , R ⁴ and R ^{5 are} independently hydrogen, (C 1 -C ₄ ) -alkyl, sulfo or chloro;

R ^{6 is} sulfo;

R ⁷ is (CrC ₄₎ alkyl, amino or (C _r C ₄₎ alkyl substituted amino by; R ^{8 is} hydrogen or (C _r C ₄ ) -alkyl;

X ¹ and X ^{2 are} independently halogen or amino; Y is vinyl or -CH ₂ CH ₂ -Z; Z is an alklisch cleavable substituent; M is hydrogen or an alkali metal; and n stands for 0, 1, 2 or 3.

(C 1 -C ₄ ) -alkyl groups may be straight-chain or branched and are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Preferred are methyl and ethyl. The same applies to (C 1 -C ₄ ) -alkoxy groups, with methoxy and ethoxy being preferred.

Halogen is in particular fluorine, chlorine and bromine.

For M standing alkali is especially lithium, sodium and potassium. Preferably, M is hydrogen or sodium.

Alkali-cleavable substituents Z are, for example, halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, such as alkylcarboxylic acids, optionally substituted benzenecarboxylic acids and optionally substituted benzenesulfonic acids, such as the alkanoyloxy groups of 2 to 5 carbon atoms, of which in particular acetyloxy, benzoyloxy, sulfobenzoyloxy , Phenylsulfonyloxy and Toluylsulfonyloxy, further acidic ester groups of inorganic acids, such as phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato), as well dialkylamino groups with alkyl groups of 1 to 4 carbon atoms, such as dimethylamino and diethylamino. The sulfato group Z is preferably vinyl, β-chloroethyl and particularly preferably β-sulfatoethyl. The groups "sulfo", "thiosulfato", "phosphato", and "sulfato" include both their acid form and their salt form. Accordingly, sulfo groups correspond to the formula -SO ₃ M, thiosulfato of formula -S-SO ₃ M, phosphato groups of the formula -OPO ₃ M ₂ and sulfato groups of the formula -OSO ₃ M, where each M is as defined above.

The dyes of the general formula (I) may have different fiber-reactive groups -SO ₂ -Y. In particular, the fiber-reactive groups SO ₂ -Y can mean, on the one hand, vinylsulfonyl groups and, on the other hand, groups -CH ₂ CH ₂ Z, preferably β-sulfatoethylsulfonyl groups. Containing the dyes of the general formula (I) partially vinylsulfonyl groups, the proportion of each dye with the vinylsulfonyl group is up to about 30 mol%, based on the respective total dye amount of the dye of the general formula (I).

R ¹ is preferably hydrogen, methyl or methoxy. R ² and R ³ are preferably hydrogen. R ⁴ is preferably hydrogen, methyl or methoxy.

R ⁵ is preferably sulfo.

R ⁷ is preferably methyl or amino. R ⁸ is preferably hydrogen or

Methyl. X ¹ is preferably fluorine or chlorine. X ² is preferably fluorine, chlorine or

Amino. n is preferably 2 or 3.

Preferred mixtures contain the dye of the general formula (Ia)

and the dye of the general formula (IIa)

_{(| | a)} wherein

Y 'for AIIyI or -CH ₂ CH ₂ OSO ₃ M' and M 'are hydrogen, sodium or potassium.

The dye mixtures according to the invention contain the dyes of the general formula (I) preferably in an amount of 1 to 99 wt .-%, particularly preferably 10 to 90 wt .-% and most preferably 25 to 75 wt .-%, and the dyes of general formulas (II) preferably in an amount of 1 to 99 wt .-%, particularly preferably 10 to 90 wt .-% and most preferably 25 to 75 wt .-%.

The dye mixtures according to the invention can be in the form of solid or liquid (dissolved) commercial forms.

In solid form, they contain, as far as necessary, the usual in water-soluble and especially fiber-reactive dyes electrolyte salts, such as sodium chloride, potassium chloride and sodium sulfate. Furthermore, they may contain the usual in commercial dyes aids, such as buffer substances that can adjust a pH in aqueous solution between 5 and 7, such as sodium acetate, sodium citrate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate and disodium hydrogen phosphate, also dyeing aids, dedusting and low Quantities of siccatives. In solid form, the dye mixtures according to the invention are generally in the form of electrolytic salt-containing powders or granules (hereinafter generally referred to as preparation) with, if appropriate, one or more of the abovementioned auxiliaries. In the preparations, the dye mixture to 20 to 90 wt .-%, based on the preparation, included. The buffer substances are generally present in a total amount of up to 5% by weight, based on the preparation.

If the dye mixtures according to the invention are present in aqueous solution, then the total dye content in these aqueous solutions is up to about 50 wt .-%, such as between 5 and 50 wt .-%, wherein the Electrolyte salt content in these aqueous solutions preferably below 10 wt .-%, based on the aqueous solution is. The aqueous solutions (liquid preparations) may contain the mentioned buffer substances usually in an amount of up to 5% by weight, preferably up to 2% by weight.

The dye mixtures according to the invention can be prepared in a simple manner by mixing the dyes of the general formulas (I) and (II) in the desired mixing ratio. The dyes can be used in the mixing process both in the form of an aqueous solution, in particular in the form of the resulting in their preparation synthesis solutions, as well as a solid substance, such as in the form of dye powders or granules. The person skilled in the art is familiar with these mixing methods.

Dyestuff mixtures according to the invention which comprise dyes of the general formula (I) which have groups of the formula SO ₂ -Y in which Y is vinyl can also be prepared from corresponding dye mixtures according to the invention in which Z is β-chloroethyl, β-thiosulfatoethyl or β- Sulfatoethyl can be obtained by the latter groups are converted with the required amount of alkali wholly or partly in vinyl. This transfer takes place in a manner familiar to the person skilled in the art.

The dye mixtures according to the invention are isolated from aqueous solution in a manner known per se by salting out, for example with common salt or potassium chloride, or by spray drying or evaporation.

The dyes of the general formulas (I) and (II) are known and are described, for example, in DE 1 282 213 (formula (I)) and GB 970475 (formula (M)), and are commercially available.

The dye mixtures according to the invention have valuable performance properties and can be used for dyeing and in particular for printing materials containing carbonamide and / or hydroxyl groups. These materials are especially in the form of fibers. Thus, the dye mixtures according to the invention for printing wool and silk and in particular of cellulose-containing fiber materials of all kinds. They are preferably also suitable for printing on blended fabrics containing carbonamide and / or hydroxyl group-containing materials. It is also possible to use the dye mixtures according to the invention to print textiles or paper by the inkjet process.

The dye mixtures according to the invention provide yellow dyeings or prints with good fastness properties in these applications.

The present invention thus also relates to the use of the dye mixtures according to the invention for dyeing or printing

Carbonamide- and / or hydroxyl-containing materials or processes for dyeing or printing such materials in per se conventional procedures, in which one uses a dye mixtures according to the invention as a colorant.

For the purposes of the present invention, the term fiber materials or fibers is understood to mean, in particular, textile fibers which may be in the form of woven, knitted or spun yarns or in the form of strands or wound bodies.

Carbonamide group-containing materials may be of synthetic or natural origin and are present in particular in the form of fibers. Examples are wool and silk.

Hydroxy-containing materials are those of natural or synthetic origin such as cellulosic fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated CeI Iu loose fibers are, for example, rayon and viscose rayon.

The dye mixtures according to the invention can be applied and fixed on the abovementioned materials, in particular on the fiber materials mentioned, according to the application techniques known for water-soluble, in particular, those known for fiber-reactive dyes. The case used for printing pastes can except the dye mixtures according to the invention and water contain further additives. Additives are, for example, wetting agents, anti-foaming agents, leveling agents and agents influencing the properties of the textile material, such as softeners and soil-, water- and oil-repellent or water-softening agents. In addition, agents which influence the rheology and the running properties, as well as weak oxidizing agents, for example anti-reduction agents. In particular, printing pastes may also contain natural or synthetic thickeners, such as alginates and cellulose ethers. In dyeing baths and printing pastes, the amounts of dye can vary within wide limits depending on the desired color depth. In general, the dyes of the general formula (I) are present in amounts of from 0.01 to 15% by weight, in particular in amounts of from 0.1 to 10% by weight, based on the dyestuff or the printing paste.

After the usual printing processes for cellulose fibers, the single phase - for example, by printing with a sodium bicarbonate or other acid-binding agent-containing printing paste and subsequent steaming at

100 to 103 ⁰ C, - or two-phase - for example, by printing with neutral or weakly acidic ink and then fixing either by passing through a hot electrolyte-containing alkaline bath or by over-padding with an alkaline electrolyte-containing padding liquor and then staying or steaming or treatment with dry heat of the alkaline padded material can be carried out, you get strong color prints with good contour and a clear white fund. The failure of the prints is only slightly dependent on changing fixing conditions.

When fixing by means of dry heat according to the usual thermofixing hot air is used from 120 to 180 ⁰ C. In addition to the usual water vapor of

101 to 103 ⁰ C, superheated steam and pressure steam of temperatures up to 175 ° C can be used.

The acid-binding and the fixing of the dyes on the cellulose fibers causing agents are, for example, water-soluble basic salts of alkali metals and also alkaline earth metals of inorganic or organic acids or compounds which release alkali in the heat. In particular, the Alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids to call, of the alkali metal compounds, preferably the sodium and potassium compounds are meant. Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or trisodium phosphate.

The prints prepared with the dye mixtures according to the invention have a high color strength and a high fiber-dye bond stability in both acidic and alkaline range, furthermore good light fastness and good wet fastness properties, such as washing, water, and perspiration fastness and good ironing fastness and rubbing fastness.

The present invention also relates to inks for digital textile printing by the ink-jet process, which are characterized in that they contain a dye mixture according to the invention.

The inks according to the invention contain the dye mixture according to the invention, for example in amounts of from 0.1% by weight to 50% by weight, preferably in amounts of from 1% by weight to 30% by weight and more preferably in amounts of 1% by weight. % to 15% by weight based on the total weight of the ink. Of course, the inks may also contain mixtures of dye mixtures according to the invention and other dyes which are used in textile printing. For the use of inks in the continuous flow process, a conductivity of 0.5 to 25 mS / m can be set by addition of electrolyte.

Suitable electrolytes are, for example: lithium nitrate, potassium nitrate.

The inks of the invention can be organic solvents with a

Total content of 1-50%, preferably from 5-30 wt .-%.

Suitable organic solvents are, for example, alcohols, for. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert. Butanol, pentyl alcohol, polyhydric alcohols z. B.: 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, e.g. B.: Polyethylene glycol, polypropylene glycol, Alkylene glycols having 2 to 8 alkylene groups, e.g. For example: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyl triglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, lower alkyl ethers of polyhydric alcohols, e.g. 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 nonyl phenyl ether,

Amines, such as Example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives such. 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 ketoalcohols, such as. B.: Acetone, diacetone alcohol, cyclic ethers, such as. B .; Tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma-butyrolactone, epsilon-caprolactam, furthermore sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane,

Dimethylsulfone, butadienesulfone, dimethylsulfoxide, dibutylsulfoxide, N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-pyrrolidone, 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, ethylpentyl ether, 1,2-dimethoxypropane and trimethylpropane. Furthermore, the inks according to the invention may contain the customary additives, such as viscosity moderators to adjust viscosities in the range of 1, 5 to 40.0 mPas in a temperature range of 20 to 50 ⁰ 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. Suitable viscosity moderators are theological additives, for example:

Polyvinylcaprolactam, polyvinylpyrrolidone and their co-polymers polyether polyol, associative thickener, polyurea, polyurethane, sodium alginates, modified galactomannans, polyether urea, polyurethane, nonionic cellulose ethers. As further additives, the inks of the invention can surface-active substances for the adjustment of surface tensions of 20 to 65 mN / m, which are optionally adjusted depending on the method used (thermal or piezo technology).

Suitable surface-active substances are, for example: surfactants of all kinds, preferably nonionic surfactants, butyldiglycol and 1,2-hexanediol. Further, the inks may still contain conventional additives such as fungicidal and bacterial growth inhibiting agents in amounts of from 0.01 to 1% by weight based on the total weight of the ink.

The inks of the invention may be prepared in the usual manner by mixing the components in water.

The inks of the invention are suitable for use in ink-jet printing processes for printing a wide variety of preprepared cellulose-containing fiber materials of all kinds, as well as silk and wool. The printing inks of the invention are also suitable for printing pretreated hydroxy-containing or amino-containing fibers contained in blend fabrics, z. As mixtures of cotton, silk, wool with polyester fibers or polyamide fibers. In contrast to conventional textile printing, in which the printing ink already contains all fixing chemicals and thickeners for a reactive dye, in the case of ink-jet printing the auxiliaries must be applied to the textile substrate in a separate pretreatment step.

The pretreatment of the textile substrate, such as cellulose and cellulose regenerated fibers and silk and wool - takes place before printing an aqueous alkaline liquor. Alkali, such as sodium carbonate, sodium bicarbonate, sodium acetate, trisodium phosphate, sodium silicate, sodium hydroxide, alkali donors such as sodium chloroacetate, sodium formate, hydrotropes such as urea, reduction inhibitors such as sodium nitrobenzenesulfonates, as well as thickening agents, the flow of the To prevent motifs when applying the ink, these are, for example, sodium alginates, modified polyacrylates or highly etherified galactomannans. These pre-preparation reagents are coated with suitable applicators, such as a 2- or 3-roll pad, with non-contact

Spray technologies, applied by foam application or with appropriately adapted inkjet technologies in a defined amount evenly on the textile substrate and then dried. After printing, the textile fiber material is dried at 120 to 150 ⁰ C and then fixed.

The fixation of the inkjet prints prepared with reactive dyes can be carried out 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 types of energy transfer. One distinguishes one- and two-phase fixation processes:

In single-phase fixation, the chemicals necessary for fixation are already on the textile substrate.

In the case of two-phase fixation, this pretreatment can be omitted. For fixing only alkali is needed, which is applied after the ink-jet printing before the fixing without intermediate drying. Other additives such as urea or thickener can be dispensed with.

After the fixation, the post-treatment is carried out, which is the prerequisite for good fastness, high brilliance and a perfect white foundation. The prints prepared with the inks of the present invention have high color strength and high fiber-dye bonding stability in both the acidic and alkaline regions, furthermore good fastness to light and good wet fastness properties such as washing, waterfastness and perspiration fastness, as well as good Ironing fastness and rubbing fastness. example 1

35 g of a dye mixture containing 45 wt.% Of the dye of the formula

(Ia) and 55 wt.% Of the dye of formula (IIa) are in 800 g of a

Incorporated stock of the following composition and water

Filled in 1000g. Stock paste:

600g alginate thickening (incl. 5g / kg polyphosphate)

100g urea

30 g of sodium bicarbonate

2 g of a commercially available defoamer 1 g of a commercially available stabilizer ad 1000 g of water

With the printing paste thus obtained, cellulosic substrates are printed in direct printing by the usual methods, in flat film printing, rotary printing, desktop printing, manual printing after the single phase or two-phase printing.

The prints obtained are dried at 100 ⁰ C, fixed and aftertreated in the usual way.

Example 2 A textile fabric consisting of mercerized cotton is treated with a

Fleet containing 35 g / l sodium carbonate kalz, 100 g / l urea and 150 g / l of a low-viscosity Na alginate solution (6%) padded and then dried. The

Fleet intake is 70%.

An aqueous ink containing 2% of a dye mixture containing 45% by weight of the dye of the formula (Ia) and 55% by weight of the dye of the formula (IIa) is applied to the textile pretreated in this way.

20% sulfolane

0.01% Mergal K9N

77.99% water printed with a drop-on-demand (bubble-jet) inkjet printhead. The print is completely dried. The fixation takes place by means of saturated steam at 102 ° C for 8 minutes. The pressure is then rinsed warm, subjected to a fastness wash with hot water at 95 ° C., rinsed warm and then dried. This gives a pressure with excellent use fastness.

Claims

claims

1. dye mixture containing at least one dye of the general formula (I)

and at least one dye of the general formula (II)

wherein

R ¹ and R ² are each independently hydrogen, (CrC ₄₎ alkyl, (C ₁ -C ₄ J -alkoxy, sulfo, chlorine or bromine;

R ³ , R ⁴ and R ⁵ independently of one another represent hydrogen, (C 1 -C ₄ ) -alkyl, sulfo or

Chlorine;

R ^{6 is} sulfo;

R ^{7 is} (C 1 -C ₄ ) -alkyl, amino or (C 1 -C ₄ ) -alkyl-substituted amino; R ^{8 is} hydrogen or (C _r C ₄ ) -alkyl;

X ¹ and X ^{2 are} independently halogen or amino;

Y is vinyl or -CH ₂ CH ₂ -Z;

Z is an alklisch cleavable substituent;

M is hydrogen or an alkali metal; and n stands for 0, 1, 2 or 3.

2. dye mixture according to claim 1, characterized in that R ^{1 is} hydrogen, methyl or methoxy; R ² and R ^{3 are} hydrogen;

R ^{4 is} hydrogen, methyl or methoxy; R ^{5 is} sulfo;

R ^{7 is} methyl or amino;

R ^{8 is} hydrogen or methyl;

X ^{1 is} fluorine or chlorine;

X ^{2 is} fluorine, chlorine or amino; n for 2 or 3;

Z is vinyl or β-sulfatoethyl; and

M stands for hydrogen or sodium.

3. dye mixture according to claim 1 and / or 2, characterized in that they contain the dye of the general formula (Ia)

and the dye of the general formula (IIa)

wherein

Y 'for AIIyI or -CH ₂ CH ₂ OSO ₃ M' and

M 'stand for hydrogen, sodium or potassium.

4. A process for the preparation of a dye mixture according to one or more of claims 1 to 3, characterized in that the dyes of the general formulas (I) and (II) are mixed together in the desired mixing ratio.

5. Use of a dye mixture according to one or more of claims 1 to 3 for dyeing or printing carbonamide and / or hydroxyl-containing materials

6. ink for digital textile printing by the ink-jet process, characterized in that it contains a dye mixture according to one or more of claims 1 to 3.