WO2004026966A1 - Dye mixtures of fibre-reactive azo dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups - Google Patents

Dye mixtures of fibre-reactive azo dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups Download PDF

Info

Publication number
WO2004026966A1
WO2004026966A1 PCT/EP2003/010190 EP0310190W WO2004026966A1 WO 2004026966 A1 WO2004026966 A1 WO 2004026966A1 EP 0310190 W EP0310190 W EP 0310190W WO 2004026966 A1 WO2004026966 A1 WO 2004026966A1
Authority
WO
WIPO (PCT)
Prior art keywords
optionally substituted
formula
alkyl
hydrogen
group
Prior art date
Application number
PCT/EP2003/010190
Other languages
French (fr)
Inventor
Werner Russ
Warren James Ebenezer
Michael Gordon Hutchings
Original Assignee
Dystar Textilfarben Gmbh & Co. Deutschland Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dystar Textilfarben Gmbh & Co. Deutschland Kg filed Critical Dystar Textilfarben Gmbh & Co. Deutschland Kg
Priority to AU2003270191A priority Critical patent/AU2003270191A1/en
Publication of WO2004026966A1 publication Critical patent/WO2004026966A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0047—Mixtures of two or more reactive azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/043—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring containing two or more triazine rings linked together by a non-chromophoric link
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/08—Azo dyes
    • C09B62/09—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
    • C09B62/24—Azo dyes
    • C09B62/25—Disazo or polyazo dyes

Definitions

  • the present invention relates to the field of fibre-reactive dyes.
  • Dyestuffs Containing chromophores linked via diethylenetriamine are known from literature and are described for example in JP 50107277.
  • dyestuffs of the general formula (I) or dyestuffs of the general formula (II) and especially mixtures of dyestuff (I) and dyestuff (II) providing exceptionally strong and economic dyes and exhibiting excellent fastness properties can be obtained if diethylenetriamine and analogues are used to link two or three chromophores each selected from a specific range of chromophores as defined below.
  • the present invention claims mixtures of fibre reactive dyes comprising one or more dyestuffs of the formula (I)
  • Ar 1 and Ar 2 are optionally substituted aryl groups, especially phenyl or naphthyl;
  • V and W are hydroxy or amino and V and W are not the same;
  • R is hydrogen, optionally substituted C C 4 alkyl or optionally substituted phenyl
  • M is H or alkali metal, especially sodium
  • G is nitrogen or a sp 2 -carbon atom substituted by H, Cl, F, CN or NO 2 ;
  • m and n are independently 2 to 6;
  • Y is a halogen radical such as fluoro, chloro or bromo or a quaternary ammonium unit
  • X is a a group R-carbonyl- or a heterocyclic fibre reactive group where R is an optionally substituted alkyl group, or optionally substituted phenyl, or optionally substituted vinyl and X may be coloured or colourless and of the form
  • A, A' and A" independently are fluorine or chlorine
  • Q is hydrogen, fluorine, chlorine, cyano or nitro and B denotes oxyalkyl of the formula OR 10 , thioalkyl of the formula SR 11 or amino NR 12 R 13 where R 10 , R 11 , R 12 is hydrogen, optionally substituted C r C 4 alkyl or optionally substituted phenyl and
  • R 13 is hydrogen, optionally substituted alkyl or optionally substituted aryl or is nitrile.
  • the group R 13 can be coloured or colourless and may consist of an azo chromophore, but NR 12 R 13 cannot be a chromophore of formula D.
  • Alkyl groups may be straight-chain or branched and are preferably (C C 4 )-alkyl groups, for example methyl, ethyl, n-propyl, i-propyl or n-butyl. Substituted alkyl groups are preferably substituted by hydroxyl, (C,-C 4 )-alkoxy, halogen or carboxyl groups and acylated amino (NR 1 COR 2 )
  • Substituents for aryl groups are preferably (C C 4 )-alkoxy, halogen, carboxyl, carbonamide, optionally substituted C C 4 -alkyl, nitrile, sulpho, sulphonamide and acylated amino (NR 1 COR 2 ) wherein
  • R 1 is H, (C C 4 )-alkyl optionally substituted with hydroxyl, (C C 4 )-alkoxy, halogen or carboxyl groups and
  • R 2 is H, (C C 4 )-alkyl optionally substituted with hydroxyl, (C C 4 )-alkoxy, halogen or carboxyl groups, a vinyl group optionally substituted with (C C 4 )- alkyl, an aryl group optionally substituted with sulpho, (C r C 4 )-alkoxy, halogen or carboxyl groups.
  • Preferred embodiments of the invention are where m and n are 2 or' 3 or 6, especially preferred 2;
  • Y is chloro or fluoro, or 3- or 4- carboxypyridinium, especially chloro;
  • X is alkylcarbonyl, vinylcarbonyl or a heterocyclic fibre reactive group (Z)
  • A is as defined above and is preferably chloro R 12 is hydrogen or optionally substituted C, to C 4 alkyl
  • R 13 is hydrogen or an aromatic or aliphatic radical optionally sulphonated, and maybe coloured or colourless , such as ⁇ - hydroxyethyl, sulfophenyl, or a group of formula Z-3
  • Ar is a phenyl or naphthyl unit, substituted by one or more sulpho groups, and optionally substituted by one or more C, to C 4 alkyl units, halogen such as fluoro, chloro or bromo, or methoxy;
  • V and W are independently hydroxy or amino under the proviso that V is different to W and
  • M is preferably H, an alkaline metal, such as sodium, potassium or lithium and is especially preferably sodium.
  • Especially preferred dyestuff mixtures of the invention comprise (1-1 )
  • the dyestuffs of the present invention can be present as a preparation in solid or liquid (dissolved) form.
  • solid form they generally contain the electrolyte salts customary in the case of water-soluble and in particular fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and also the auxiliaries customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 8, such as sodium acetate, sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogenphosphate and disodium hydrogenphosphate, small amounts of siccatives or, if they are present in liquid, aqueous solution (including the presence of ' thickeners of the type customary in print pastes), substances which ensure the permanence of these preparations, for example mold preventatives.
  • the azo dyestuffs of the formula (1) are contained in the mixture in quantity of 1 0-50% by weight and the azo dyestuffs of the formula (II) are contained in the mixture in a mixing ratio of 1 0-50% by weight, preferably in a mixing ration of 20% by weight to 40% by weight.
  • the dyestuffs of the present invention are present as dye powders containing 1 0 to 80% by weight, based on the dye powder or preparation, of a strength-standardizing colorless diluent electrolyte salt, such as those mentioned above.
  • These dye powders may additionally include the aforementioned buffer substances in a total amount of up to 1 0%, based on the dye powder. If the dye mixtures of the present invention are present in aqueous solution, the total dye content of these aqueous solutions is up to about 50 % by weight, for example between 5 and 50% by weight, and the electrolyte salt content of these aqueous solutions will preferably be below 1 0% by weight, based on the aqueous solutions.
  • the aqueous solutions (liquid preparations) may include the aforementioned buffer substances in an amount which is generally up to 1 0% by weight, for example 0.1 to 10% by weight, preference being given to up to 4% by weight, especially 2 to 4% by weight.
  • a dyestuff mixture comprising dyestuff of the formula (I) and dyestuff of the formula (II) may for example be prepared by reacting dialkylenetriamine with dichlorotriazinyl dyes of formula (V)
  • the compounds of the formula (V) based on the radicals (III) and (IV) can be prepared for example by means of customary diazotization and coupling reactions in a manner familiar to those skilled in the art.
  • reaction of diethylenetriamine with a solution of the navy dichlorotriazinyl dye (V-1 ) followed by addition of acetic anhydride to the reaction mixture gives an approximate 1 : 1 ratio of dyestuffs of the general formula (1-1 ) and dyestuffs of the general formula (11-1 ) where Y is chloro and X is acetyl.
  • the dyestuffs and dyestuff mixtures of the instant invention are reactive dyestuffs suitable for dyeing and printing hydroxy- and/or carboxamido- containing fibre materials by the application and fixing methods numerously described in the art for fibre-reactive dyes. They provide exceptionally strong and economic shades. Such dyes especially when used for exhaust dyeing of cellulosic materials can exhibit excellent properties including build-up, aqueous solubility, light-fastness, wash off and robustness to process variables. They are also wholly compatible with similar dyes designed for high temperature (80- 100° C) application to cellulosic textiles, and thus lead to highly reproducible application processes, with short application times.
  • the present invention therefore also provides for use of the inventive dyestuffs for dyeing and printing hydroxy- and/or carboxamido-containing fibre materials and processes for dyeing and printing such materials using a dyestuff according to the invention.
  • the dyestuff is applied to the substrate in dissolved form and fixed on the fibre by the action of an alkali or by heating or both.
  • Hydroxy-containing materials are natural or synthetic hydroxy-containing materials, for example cellulose fiber materials, including in the form of paper, or their regenerated products and polyvinyl alcohols.
  • Cellulose fiber materials are preferably cotton but also other natural vegetable fibers, such as linen, hemp, jute and ramie fibres.
  • Regenerated cellulose fibers are for example staple viscose and filament viscose.
  • 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-1 1 , and nylon-4.
  • inventive dyestuffs is by generally known processes for dyeing and printing fiber materials by the known application techniques for fibre- reactive dyes.
  • the dyestuffs according to the invention are highly compatible with similar dyes designed for high temperature (80-1 00° C) applications and are advantageously useful in exhaust dyeing processes.
  • the conventional printing processes for cellulose fibers which can either be carried out in single-phase, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and the colorant, and subsequent steaming at appropriate temperatures, or in two phases, for example by printing with a neutral or weakly acid print paste containing the colorant and subsequent fixation 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 of this treated material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well defined contours and a clear white ground. Changing fixing conditions has only little effect on the outcome of the prints.
  • the hot air used in dry heat fixing by the customary thermofix processes has a temperature of from 1 20 to 200°C.
  • the customary steam at from 101 to 103°C, it is also possible to use superheated steam and high pressure steam at up to 1 60°C.
  • inventive dyestuffs can in addition be used to produce inks useful for printing the substrates described above, for example textiles, especially cellulosic textiles, and paper.
  • inks can be used in all technologies, for example conventional printing, ink-jet printing or bubble-jet printing (for information on such printing technologies see for example Text. Chem. Color, Volume 1 9(8), pages 23 ff and Volume 21 , pages 27 ff) .
  • Acid-binding agents responsible for fixing the dyes to cellulose fibers are for example water-soluble basic salts of alkali metals and of alkaline earth metals of inorganic or organic acids, and compounds, which release alkali when hot.
  • alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids 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.
  • These acid-binding agents are for example so'dium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate and disodium hydrogenphosphate.
  • the dyeings on cellulose after they have been given the usual aftertreatment of rinsing to remove unfixed dye portions, show excellent properties.
  • the dyeings of polyurethane and polyamide fibers are customarily carried out from an acid medium.
  • the dyebath may contain for example acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate to bring it to the desired pH.
  • customary leveling auxiliaries for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or based on a reaction product of for example stearylamine with ethylene oxide.
  • the material to be dyed is introduced into the bath at a temperature of about 40°C and agitated therein for some time, the dyebath is then adjusted to the desired weakly acid, preferably weakly acetic acid, pH, and the actual dyeing is carried out at temperature between 60 and 98°C.
  • the dyeings can also be carried out at the boil or at temperatures up to 1 20°C (under superatmospheric pressure) .
  • the examples herein below serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight relate to r parts by volume as the kilogram relates to the liter.
  • the compounds described in the examples in terms of a formula are indicated in the form of the free sulphonic acids, but as in general they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used for dyeing in the form of these salts.
  • the starting compounds and components mentioned in the form of the free acid in the examples hereinbelow may be used in the synthesis as such or similarly in the form of their salts, preferably alkali metal salts.
  • Diethylenetriamine (0.74g, 0.007 mol) was added in one portion to a stirred solution of the navy dichlorotriazinyl dye (VI) (0.007 mol) in water (400 ml) at ambient temperature and pH8.5. The pH was then maintained at 8.5 with sodium carbonate solution for 30 minutes. More navy dichorotriazine dye

Abstract

The present invention refers to mixtures of water soluble fibre reactive dyes comprising one or more dyestuffs of the formula (I), and one or more dyestuffs of the formula (II), where chromophores of formula D have the general structure (III) and G, Ar1, Ar2, Y, X, V, W, m, n and M are as defined in claim 1.

Description

Dye Mixtures Of Fibre-Reactive Azo Dyes And Use Thereof For Dyeing Material Containing Hydroxy- And/Or Carboxamido Groups
The present invention relates to the field of fibre-reactive dyes.
Dyestuffs Containing chromophores linked via diethylenetriamine are known from literature and are described for example in JP 50107277.
The inventors of the present invention have surprisingly found that dyestuffs of the general formula (I) or dyestuffs of the general formula (II) and especially mixtures of dyestuff (I) and dyestuff (II) providing exceptionally strong and economic dyes and exhibiting excellent fastness properties, can be obtained if diethylenetriamine and analogues are used to link two or three chromophores each selected from a specific range of chromophores as defined below.
The present invention claims mixtures of fibre reactive dyes comprising one or more dyestuffs of the formula (I)
Figure imgf000002_0001
and one or more dyestuffs of the formula (II)
Figure imgf000003_0001
and especially mixtures of dyestuffs (I) and (II)
where (I) and (II) are water soluble reactive dyes and chromophores of formula D have the general structure
Figure imgf000003_0002
where
Ar1 and Ar2 are optionally substituted aryl groups, especially phenyl or naphthyl;
V and W are hydroxy or amino and V and W are not the same;
R is hydrogen, optionally substituted C C4 alkyl or optionally substituted phenyl;
M is H or alkali metal, especially sodium, G is nitrogen or a sp2-carbon atom substituted by H, Cl, F, CN or NO2; m and n are independently 2 to 6;
Y is a halogen radical such as fluoro, chloro or bromo or a quaternary ammonium unit;
X is a a group R-carbonyl- or a heterocyclic fibre reactive group where R is an optionally substituted alkyl group, or optionally substituted phenyl, or optionally substituted vinyl and X may be coloured or colourless and of the form
Figure imgf000004_0001
where A, A' and A" independently are fluorine or chlorine,
Q is hydrogen, fluorine, chlorine, cyano or nitro and B denotes oxyalkyl of the formula OR10, thioalkyl of the formula SR11 or amino NR12R13 where R10, R11 , R12 is hydrogen, optionally substituted CrC4 alkyl or optionally substituted phenyl and
R13 is hydrogen, optionally substituted alkyl or optionally substituted aryl or is nitrile. The group R13 can be coloured or colourless and may consist of an azo chromophore, but NR12R13 cannot be a chromophore of formula D.
Alkyl groups may be straight-chain or branched and are preferably (C C4)-alkyl groups, for example methyl, ethyl, n-propyl, i-propyl or n-butyl. Substituted alkyl groups are preferably substituted by hydroxyl, (C,-C4)-alkoxy, halogen or carboxyl groups and acylated amino (NR1COR2)
Substituents for aryl groups are preferably (C C4)-alkoxy, halogen, carboxyl, carbonamide, optionally substituted C C4-alkyl, nitrile, sulpho, sulphonamide and acylated amino (NR1COR2) wherein
R1 is H, (C C4)-alkyl optionally substituted with hydroxyl, (C C4)-alkoxy, halogen or carboxyl groups and
R2 is H, (C C4)-alkyl optionally substituted with hydroxyl, (C C4)-alkoxy, halogen or carboxyl groups, a vinyl group optionally substituted with (C C4)- alkyl, an aryl group optionally substituted with sulpho, (CrC4)-alkoxy, halogen or carboxyl groups.
Preferred embodiments of the invention are where m and n are 2 or' 3 or 6, especially preferred 2;
Y is chloro or fluoro, or 3- or 4- carboxypyridinium, especially chloro;
X is alkylcarbonyl, vinylcarbonyl or a heterocyclic fibre reactive group (Z)
R12 /
V3
A (Z) where
A is as defined above and is preferably chloro R12 is hydrogen or optionally substituted C, to C4 alkyl
R13 is hydrogen or an aromatic or aliphatic radical optionally sulphonated, and maybe coloured or colourless , such as β- hydroxyethyl, sulfophenyl, or a group of formula Z-3
Figure imgf000005_0001
Z-3 wherein M is as defined above; and the chromophoric units. D are based on the chromophore of formula (III)
Figure imgf000006_0001
or especially preferably based on the chromophore of formula (IV)
Figure imgf000006_0002
wherein
Ar is a phenyl or naphthyl unit, substituted by one or more sulpho groups, and optionally substituted by one or more C, to C4 alkyl units, halogen such as fluoro, chloro or bromo, or methoxy;
V and W are independently hydroxy or amino under the proviso that V is different to W and
M is preferably H, an alkaline metal, such as sodium, potassium or lithium and is especially preferably sodium.
Especially preferred dyestuff mixtures of the invention comprise (1-1 )
Figure imgf000007_0001
and (11-1 ;
Figure imgf000007_0002
(11-1)
or (1-2)
Figure imgf000007_0003
(I-2)
and (II-2)
Figure imgf000008_0001
1-2)
wherein Ar, V, W, X, Y and M are as defined above.
The dyes of formulae (I) and (II) where m = n = 2 are derived from cheap diethylenetriamine according to formula (1 ) .
NH,CH,CH,NHCH,CH,NH, ( 1 )
The dyestuffs of the present invention can be present as a preparation in solid or liquid (dissolved) form. In solid form they generally contain the electrolyte salts customary in the case of water-soluble and in particular fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and also the auxiliaries customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 8, such as sodium acetate, sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogenphosphate and disodium hydrogenphosphate, small amounts of siccatives or, if they are present in liquid, aqueous solution (including the presence of'thickeners of the type customary in print pastes), substances which ensure the permanence of these preparations, for example mold preventatives.
The azo dyestuffs of the formula (1) are contained in the mixture in quantity of 1 0-50% by weight and the azo dyestuffs of the formula (II) are contained in the mixture in a mixing ratio of 1 0-50% by weight, preferably in a mixing ration of 20% by weight to 40% by weight.
In general, the dyestuffs of the present invention are present as dye powders containing 1 0 to 80% by weight, based on the dye powder or preparation, of a strength-standardizing colorless diluent electrolyte salt, such as those mentioned above. These dye powders may additionally include the aforementioned buffer substances in a total amount of up to 1 0%, based on the dye powder. If the dye mixtures of the present invention are present in aqueous solution, the total dye content of these aqueous solutions is up to about 50 % by weight, for example between 5 and 50% by weight, and the electrolyte salt content of these aqueous solutions will preferably be below 1 0% by weight, based on the aqueous solutions. The aqueous solutions (liquid preparations) may include the aforementioned buffer substances in an amount which is generally up to 1 0% by weight, for example 0.1 to 10% by weight, preference being given to up to 4% by weight, especially 2 to 4% by weight.
A dyestuff mixture comprising dyestuff of the formula (I) and dyestuff of the formula (II) may for example be prepared by reacting dialkylenetriamine with dichlorotriazinyl dyes of formula (V)
Figure imgf000009_0001
(V) followed by reaction with X-CI or X-OCOR .
The compounds of the formula (V) based on the radicals (III) and (IV) can be prepared for example by means of customary diazotization and coupling reactions in a manner familiar to those skilled in the art.
Thus reaction of diethylenetriamine with a solution of the navy dichlorotriazinyl dye (V-1 )
Figure imgf000010_0001
followed by addition of acetic anhydride to the reaction mixture gives an approximate 1 : 1 ratio of dyestuffs of the general formula (1-1 ) and dyestuffs of the general formula (11-1 ) where Y is chloro and X is acetyl.
i The dyestuffs and dyestuff mixtures of the instant invention are reactive dyestuffs suitable for dyeing and printing hydroxy- and/or carboxamido- containing fibre materials by the application and fixing methods numerously described in the art for fibre-reactive dyes. They provide exceptionally strong and economic shades. Such dyes especially when used for exhaust dyeing of cellulosic materials can exhibit excellent properties including build-up, aqueous solubility, light-fastness, wash off and robustness to process variables. They are also wholly compatible with similar dyes designed for high temperature (80- 100° C) application to cellulosic textiles, and thus lead to highly reproducible application processes, with short application times.
The present invention therefore also provides for use of the inventive dyestuffs for dyeing and printing hydroxy- and/or carboxamido-containing fibre materials and processes for dyeing and printing such materials using a dyestuff according to the invention. Usually the dyestuff is applied to the substrate in dissolved form and fixed on the fibre by the action of an alkali or by heating or both.
Hydroxy-containing materials are natural or synthetic hydroxy-containing materials, for example cellulose fiber materials, including in the form of paper, or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton but also other natural vegetable fibers, such as linen, hemp, jute and ramie fibres. Regenerated cellulose fibers are for example staple viscose and filament viscose. 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-1 1 , and nylon-4.
Application of the inventive dyestuffs is by generally known processes for dyeing and printing fiber materials by the known application techniques for fibre- reactive dyes. The dyestuffs according to the invention are highly compatible with similar dyes designed for high temperature (80-1 00° C) applications and are advantageously useful in exhaust dyeing processes.
Similarly, the conventional printing processes for cellulose fibers, which can either be carried out in single-phase, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and the colorant, and subsequent steaming at appropriate temperatures, or in two phases, for example by printing with a neutral or weakly acid print paste containing the colorant and subsequent fixation 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 of this treated material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well defined contours and a clear white ground. Changing fixing conditions has only little effect on the outcome of the prints. Not only in dyeing but also in printing the degrees of fixation obtained with dye mixtures of the invention are very high. The hot air used in dry heat fixing by the customary thermofix processes has a temperature of from 1 20 to 200°C. In addition to the customary steam at from 101 to 103°C, it is also possible to use superheated steam and high pressure steam at up to 1 60°C.
The inventive dyestuffs can in addition be used to produce inks useful for printing the substrates described above, for example textiles, especially cellulosic textiles, and paper. Such inks can be used in all technologies, for example conventional printing, ink-jet printing or bubble-jet printing (for information on such printing technologies see for example Text. Chem. Color, Volume 1 9(8), pages 23 ff and Volume 21 , pages 27 ff) .
Acid-binding agents responsible for fixing the dyes to cellulose fibers are for example water-soluble basic salts of alkali metals and of alkaline earth metals of inorganic or organic acids, and compounds, which release alkali when hot. Of particular suitability 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. These acid-binding agents are for example so'dium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate and disodium hydrogenphosphate.
Treating the dyestuffs according to the invention with the acid-binding agents, with or without heating, bonds the dyes chemically to the cellulose fibers. Especially the dyeings on cellulose, after they have been given the usual aftertreatment of rinsing to remove unfixed dye portions, show excellent properties.
The dyeings of polyurethane and polyamide fibers are customarily carried out from an acid medium. The dyebath may contain for example acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate to bring it to the desired pH. To obtain a dyeing of acceptable levelness it is advisable to add customary leveling auxiliaries, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or based on a reaction product of for example stearylamine with ethylene oxide. In general the material to be dyed is introduced into the bath at a temperature of about 40°C and agitated therein for some time, the dyebath is then adjusted to the desired weakly acid, preferably weakly acetic acid, pH, and the actual dyeing is carried out at temperature between 60 and 98°C. However, the dyeings can also be carried out at the boil or at temperatures up to 1 20°C (under superatmospheric pressure) . The examples herein below serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight relate to r parts by volume as the kilogram relates to the liter. The compounds described in the examples in terms of a formula are indicated in the form of the free sulphonic acids, but as in general they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used for dyeing in the form of these salts. The starting compounds and components mentioned in the form of the free acid in the examples hereinbelow may be used in the synthesis as such or similarly in the form of their salts, preferably alkali metal salts.
Example 1
Diethylenetriamine (0.74g, 0.007 mol) was added in one portion to a stirred solution of the navy dichlorotriazinyl dye (VI) (0.007 mol) in water (400 ml) at ambient temperature and pH8.5. The pH was then maintained at 8.5 with sodium carbonate solution for 30 minutes. More navy dichorotriazine dye
(0.007mol) in water (400 ml) was then added to the reaction mixture over 6 hrs maintaining the solution at pH 8.5 and ambient temperature. The pH was adjusted and maintained at 9 whilst an excess of acetic anhydride was added. Subsequent chromatography indicated complete reaction to yield an approximate 1 : 1 ratio of the two products (VII) and (VIII). The reaction mixture was adjusted to pH 6 with 2N HCl and the dye precipitated by the addition of methylated spirits.
The precipitated dye was filtered off, and dried (λmax = 624.5nm).
Figure imgf000014_0001
(VI)
1) pH 8.5 20°C
2)Ac20 20°C
Figure imgf000014_0002
Following exactly analogous procedures the following dyes (examples 2 - 27) were synthesized giving 1 :1 mixtures of the respective dyestuff (IX) and (X)
Figure imgf000014_0003
(IX) and (X)
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Compounds derived from H2N(CH2)2NH(CH2)3NH2
Figure imgf000017_0002
Figure imgf000018_0001

Claims

What is claimed is:
1 . Mixtures of water soluble fiber reactive dyes comprising one or more dyestuffs of the formula (I)
Figure imgf000019_0001
and one or more dyestuffs of the formula (II)
Figure imgf000019_0002
where chromophores of formula D have the general structure
Figure imgf000019_0003
wherein
Ar1 and Ar2 are unsubstituted or aryl groups substituted by (Cϊ-C^-alkoxy, halogen, carboxyl, carbonamide, optionally substituted C C4-alkyl, nitrile, sulpho, sulphonamide and acylated amino (NR1COR2), especially phenyl or naphthyl wherein
R1 is H, (C C4)-alkyl optionally substituted with hydroxyl, (CrC4)-alkoxy, halogen or carboxyl groups and
R2 is H, (C,-C4)-alkyl optionally substituted with hydroxyl, (C.,-C4)-alkoxy, halogen or carboxyl groups, a vinyl group optionally substituted with (C
C4)-alkyl, an aryl group optionally substituted with sulpho, (C,-C4)~alkoxy, halogen or carboxyl groups.
V and W are hydroxy or amino and V and W are not the same; R is hydrogen, optionally substituted C,-C4 alkyl or optionally substituted phenyl;
M is H or alkali metal, especially sodium, G is nitrogen or a sp2-carbon atom substituted by H, Cl, F, CN or NO2 m and n are independently 2 to 6; Y is a halogen radical such as fluoro, chloro or bromo or a quaternary ammonium unit such as carboxypyridinium; X is a group R-carbonyl- or a heterocyclic fibre reactive group where R is an optionally substituted alkyl group, or optionally substituted phenyl, or optionally substituted vinyl and X may be coloured or colourless and of the form (Z)
Figure imgf000020_0001
where
A, A' and A" independently are fluorine or chlorine,
Q is hydrogen, fluorine, chlorine, cyano or nitro and
B denotes oxyalkyl of the formula OR10, thioalkyl of the formula SR1 1 or amino NR12R13 where
R10, R11, R12 is hydrogen, optionally substituted C C4 alkyl or optionally substituted phenyl and
R13 is hydrogen, optionally substituted alkyl or optionally substituted aryl, or nitrile and the group R13 can be coloured or colourless and may consist of an azo chromophore, but -NR 2R13 cannot be a chromophore of formula D.
2. Dye mixture according to claim 1 wherein
Y is chloro or fluoro, or 3- or 4- carboxypyridinium, especially chloro
X is alkylcarbonyl, vinylcarbonyl or a heterocyclic fibre reactive group (Z)
Figure imgf000021_0001
where
A is as defined above and is preferably chloro R12 is hydrogen or optionally substituted C., to C4 alkyl R13 is hydrogen or an aromatic or aliphatic radical optionally sulphonated, and may be coloured or colourless , such as β- hydroxyethyl, sulfophenyl, or a group of formula Z-3
Figure imgf000021_0002
Z-3 wherein M is as defined in claim 1 and the chromophoric units D are based on the chromophore of formula (111)
Figure imgf000022_0001
or especially preferably based on the chromophore of formula (IV)
Figure imgf000022_0002
wherein
Ar is a phenyl or naphthyl unit, substituted by one or more sulpho groups, and optionally substituted by one or more C, to C4 alkyl units, halogen such as fluoro, chloro or bromo, or methoxy; V and W are independently hydroxy or amino under the proviso that V is different to W and M is preferably H, an alkaline metal, such as sodium, potassium or lithium and is especially preferably sodium.
A dye mixture according to at least one of the claims 1 or 2 wherein a dye of formula (I) is present in the mixture in an amount of from 30 to 70% by weight and a dye of the formula (II) is present in the mixture in an amount of from 70 to 30% by weight.
4. A process for the preparation of the dye mixtures according to at least one of the claims 1 to 3 by reacting dialkylenetriamine with dichlorotriazinyl dyes of formula (V)
Figure imgf000023_0001
(V) followed by reaction with X-CI or X-OCOR wherein X is as defined in claim 1 .
5. A water soluble reactive dye of the general formula (I)
Figure imgf000023_0002
where chromophores of formula D have the general structure
Figure imgf000023_0003
wherein
Ar1 and Ar2 are optionally substituted aryl groups, especially phenyl or naphthyl;.
V and W are hydroxy or amino and V and W are not the same;
R is hydrogen, optionally substituted CrC4 alkyl or optionally substituted phenyl;
M is H or alkali metal, especially sodium, G is nitrogen or a sp2-carbon atom substituted by H, Cl, F, CN or NO2; m and n are independently 2 to 6; Y is a halogen radical such as fluoro, chloro or bromo or a quatemaryammonium unit such as carboxypyridinium; X is a group R-carbonyl- or a heterocyclic fibre reactive group where
R is an 'optionally substituted alkyl group, or optionally substituted phenyl, or optionally substituted vinyl and X may be coloured or colourless and of the form (Z)
Figure imgf000024_0001
where
A, A' and A" independently are fluorine or chlorine, Q is hydrogen, fluorine, chlorine cyano or nitro and
B denotes oxyalkyl of the formula OR10, thioalkyl of the formula
SR11 or amino NR12R13 where
R10, R11, R12 is hydrogen, optionally substituted CrC4 alkyl or optionally substituted phenyl and
R13 is hydrogen, optionally substituted alkyl or optionally substituted aryl or nitrile and the group R13 can be coloured or colourless and may consist of an azo chromophore, but -NR12R13 cannot be a chromophore of formula D.
6. A water soluble reactive dyestuff of the general formula (II)
Figure imgf000025_0001
where chromophores of formula D have the general structure
Figure imgf000025_0002
wherein
Ar1 and Ar2 are optionally substituted aryl groups, especially phenyl or naphthyl;
V and W are hydroxy or amino and V and W are not the same; R is hydrogen, optionally substituted C C4 alkyl or optionally substituted phenyl;
M is H or alkali metal, especially sodium, G is nitrogen or a sp2-carbon atom substituted by H, Cl, F, CN or NO2; m and n are independently 2 to 6; Y is a halogen radical such as fluoro, chloro or bromo or a quaternary ammonium unit such as carboxypyridinium; X is a group R-carbonyl- or a heterocyclic fibre reactive group where
R is an optionally substituted alkyl group, or optionally substituted phenyl, or optionally substituted vinyl and X may be coloured or colourless and of the form (Z)
Figure imgf000025_0003
where
A, A' and A" independently are fluorine or chlorine, Q is hydrogen, fluorine, chlorine, cyano or nitro and B denotes oxyalkyl of the formula OR10, thioalkyl of the formula
SR11 or amino NR12R13 where
R10, R11, R12 is hydrogen, optionally substituted C C4 alkyl or optionally substituted phenyl and R13 is hydrogen, optionally substituted alkyl or optionally substituted aryl or nitrile and the group R13 can be coloured or colourless and may consist of an azo chromophore, but -NR12R13 cannot be a chromophore of formula D.
process for dyeing hydroxy- and/or carboxamido - containing fiber material, in which dyestuffs or dyestuff mixtures are applied to the material and the dyes are fixed to the material by means of heat or with the aid of an alkali or by means of heat and with the aid of an alkali, which comprises dye mixtures or dyestuffs as claimed in one or more of the claims 1 to 6.
PCT/EP2003/010190 2002-09-20 2003-09-13 Dye mixtures of fibre-reactive azo dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups WO2004026966A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003270191A AU2003270191A1 (en) 2002-09-20 2003-09-13 Dye mixtures of fibre-reactive azo dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0221907.9 2002-09-20
GB0221907A GB0221907D0 (en) 2002-09-20 2002-09-20 Dye mixtures of fibre-reactive azo dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups

Publications (1)

Publication Number Publication Date
WO2004026966A1 true WO2004026966A1 (en) 2004-04-01

Family

ID=9944492

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/010190 WO2004026966A1 (en) 2002-09-20 2003-09-13 Dye mixtures of fibre-reactive azo dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups

Country Status (4)

Country Link
AU (1) AU2003270191A1 (en)
GB (1) GB0221907D0 (en)
TW (1) TW200407395A (en)
WO (1) WO2004026966A1 (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4148790A (en) * 1973-05-24 1979-04-10 Sumitomo Chemical Company Limited Metallized triazine reactive dyes
CH651583A5 (en) * 1979-12-06 1985-09-30 Sandoz Ag Halotriazinyldisazo compounds, preparation thereof, and process for dyeing leather
WO1993018224A1 (en) * 1992-03-06 1993-09-16 Ciba-Geigy Ag Process for the dyeing of cellulose-containing fibre materials with reactive dyes
EP0625551A1 (en) * 1993-05-17 1994-11-23 Ciba-Geigy Ag Mixtures of dyes, process for their preparation and the use thereof
US5821347A (en) * 1995-12-22 1998-10-13 Dy Star Textil Farben Gmbh & Co. Deutschland Kg Water-soluble azo dyestuffs, processes for their preparation and their use
WO1999005224A1 (en) * 1997-07-25 1999-02-04 Basf Aktiengesellschaft Reactive dyes containing piperazine
WO2000008104A1 (en) * 1998-07-31 2000-02-17 Basf Aktiengesellschaft Reactive dyes containing a linkage
WO2000046309A1 (en) * 1999-02-05 2000-08-10 Ciba Specialty Chemicals Holding Inc. Black-dyeing inks and their use
EP1127923A2 (en) * 1996-12-10 2001-08-29 DyStar Textilfarben GmbH & Co. Deutschland KG Water-soluble fibre-reactive dyestuffs, process for their preparation and their use

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4148790A (en) * 1973-05-24 1979-04-10 Sumitomo Chemical Company Limited Metallized triazine reactive dyes
CH651583A5 (en) * 1979-12-06 1985-09-30 Sandoz Ag Halotriazinyldisazo compounds, preparation thereof, and process for dyeing leather
WO1993018224A1 (en) * 1992-03-06 1993-09-16 Ciba-Geigy Ag Process for the dyeing of cellulose-containing fibre materials with reactive dyes
EP0625551A1 (en) * 1993-05-17 1994-11-23 Ciba-Geigy Ag Mixtures of dyes, process for their preparation and the use thereof
US5821347A (en) * 1995-12-22 1998-10-13 Dy Star Textil Farben Gmbh & Co. Deutschland Kg Water-soluble azo dyestuffs, processes for their preparation and their use
EP1127923A2 (en) * 1996-12-10 2001-08-29 DyStar Textilfarben GmbH & Co. Deutschland KG Water-soluble fibre-reactive dyestuffs, process for their preparation and their use
WO1999005224A1 (en) * 1997-07-25 1999-02-04 Basf Aktiengesellschaft Reactive dyes containing piperazine
WO2000008104A1 (en) * 1998-07-31 2000-02-17 Basf Aktiengesellschaft Reactive dyes containing a linkage
WO2000046309A1 (en) * 1999-02-05 2000-08-10 Ciba Specialty Chemicals Holding Inc. Black-dyeing inks and their use

Also Published As

Publication number Publication date
TW200407395A (en) 2004-05-16
AU2003270191A1 (en) 2004-04-08
GB0221907D0 (en) 2002-10-30

Similar Documents

Publication Publication Date Title
JPS5848672B2 (en) Dyeing method for cellulose fibers
US6359121B1 (en) Reactive dyes containing a linkage
US20010044527A1 (en) Fiber-reactive disazo compounds
EP2000511B1 (en) Trisazo reactive dyestuff compound
JPH0218707B2 (en)
JP2523671B2 (en) Water-soluble reactive dyes and dyeing methods for textile materials
CA2446784C (en) Fibre reactive scarlet azo dyes
CA2417234A1 (en) Yellow reactive monoazo dyes, methods for their preparation and use thereof
EP1380621B1 (en) Fibre reactive azo dyes
KR890001784B1 (en) Process for the manufacture of monoazo compounds
US20030191293A1 (en) Reactive dyes containing a halobenzene nucleus
EP1514905B1 (en) High light fastness reactive red dyes
EP1179034B1 (en) Mixtures of symmetrical and unsymmetrical red reactive dyes
JP2002532606A (en) Fiber reactive disazo dye
WO2004026966A1 (en) Dye mixtures of fibre-reactive azo dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups
MXPA00009743A (en) Dye mixtures of fiber-reactive azo dyes and use thereof for dyeing material containing hydroxy-and/or carboxamido groups.
EP1506981B1 (en) Fibre reactive azo dyes
WO2004041941A1 (en) Dye mixtures of fibre-reactive azo dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups
CA2428086A1 (en) Black dye mixtures of fiber-reactive azo dyes, methods for their preparation and use thereof for dyeing hydroxy- and/or carboxamido-containing fiber material
WO2005005551A1 (en) Water-soluble macrocyclic azacalixarenes
US5371200A (en) Fibre-reactive formazan dyes, processes for their preparation and their use
KR20000077295A (en) Novel brilliant yellow fluorotriazine dyes, preparation thereof and use thereof for dyeing hydroxyl- and amido-containing materials
JP2005509714A (en) Fiber reactive azo dye
JPH059396A (en) Reactive dye composition and dyeing or printing method for textile material or leather using the same
JPH0335433B2 (en)

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP