CA2370403A1 - Deep navy dye mixtures of fiber-reactive azo dyes and a method for their preparation and a process for dyeing hydroxy and/or carboxamido containing fibers - Google Patents
Deep navy dye mixtures of fiber-reactive azo dyes and a method for their preparation and a process for dyeing hydroxy and/or carboxamido containing fibers Download PDFInfo
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- CA2370403A1 CA2370403A1 CA002370403A CA2370403A CA2370403A1 CA 2370403 A1 CA2370403 A1 CA 2370403A1 CA 002370403 A CA002370403 A CA 002370403A CA 2370403 A CA2370403 A CA 2370403A CA 2370403 A1 CA2370403 A1 CA 2370403A1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive 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
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
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- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention comprises a dye mixture comprising one or more, such a s one, two or three, disazo dyes conforming to general formula (1), one or mor e, such as one, two or three, monoazo dyes conforming to general formula (2), i n which (1) and (2) are defined as given in claim 1, a method for its preparation and a process for dyeing hydroxy- and/or carboxamido containing fiber material in which an inventive dye is applied to the material.
Description
Description Deep Navy Dye Mixtures of Fiber-Reactive Azo Dyes and A Method for their Preparation and A Process for Dyeing Hydroxy and/or Carboxamido Containing Fibers The present invention relates to the field of fiber-reactive dyes.
io Navy-dyeing mixtures of fiber-reactive dyes are known from European Patent Applications EP-A 0588257, EP-A 0668328, EP-A 0127456. However these dye mixtures have still some deficiencies, such as, for ex., when applied to substrates other than cellulose, for example wool. Deep navy shades on carboxamido is containing fibers are usually achieved by the application of mordant dyes.
Mordant dyes are well known for their good fastness - and dyeing properties. However they have ecological disadvantages, so that alternative reactive dye mixtures are desirable.
2o With the present invention, deep navy-dyeing reactive dye mixtures have been found which unexpectedly and surprisingly have improved properties, such as improved resistance to ammonium aftertreatment and levelness in regard to the dyeing of wool. The present invention discloses dye mixtures comprising one or more, such as one, two or three, disazo dyes conforming to the general formula (1 ) R~ R3 Y~ - 02S \ N = N / I \ N = N I S02 - Y2 R ~ MO3S \ ~ SO3M R4 (1 ) one or more, such as one, two, three or four, monoazo dyes conforming to the general formula (2), SUBSTITUTE SHEET (R ULE 26) X~
i~ ~N
(Ya'SOZ)n D~N ~N~Xz Rs~ O H H N
(2) M03S ~ ~ S03M
in which:
R' is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably s methoxy or hydrogen and in particular hydrogen;
R2 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably hydrogen;
R3 has one of the meanings of R1 R4 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably io hydrogen;
R5 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy, sulfo or hydrogen and in particular sulfo;
R6 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy, sulfo or hydrogen and in particular sulfo;
is D is a benzene or naphthalene radical;
n is0or1 X' is a fluoro, chloro, cyanamido, or morpholino group or a group of the following formulae; NR7R$ or OR9 or wherein R»
zo *~
N SOZ Ys Rio R' is hydrogen, methyl, ethyl, hydroxyethyl, methoxyethyl, ethoxyethyl, or 2s sulfoethyl, preferably ethyl, methoxyethyl, sulfoethyl SUBSTITUTE SHEET (RULE 26) R8 has one of the meanings of R';
R9 has one of the meanings of R7;
R' has one of the meanings of R';
R" is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably s methoxy or hydrogen and in particular hydrogen;
R'2 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy or hydrogen and in particular hydrogen;
X2 has one of the meanings of X';
Y' is vinyl, or is ethyl substituted in the ~i-position by a substituent which is io eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphato, sulfobenzoyloxy and p-toluylsulfonyloxy, and Y' is preferably vinyl, f3-chloroethyl, f3-thiosulfatoethyl or f3-sulfatoethyl and is in particular preferably vinyl or ~i-sulfatoethyl;
is Y2 has one of the meanings of Y';
Y3 has one of the meanings of Y';
Y4 has one of the meanings of Y';
M denotes hydrogen or an alkali metal such as lithium, sodium and potassium.
Both in the formulae mentioned above and in those below, the individual formula members, both with different and with the same designation within a formula or the various formulae, can within the scope of their definitions have meanings which are the same as or different from one another.
The groups "sulfo", "thiosulfato", "carboxy", "phosphato" and "sulfato"
include both the acid form and the salt form of these groups. Accordingly, sulfo groups are groups of the formula -S03M' , thiosulfato groups are groups of the formula -S-S03M , carboxy groups are groups of the formula -COOM , phosphato groups are groups of the formula -OP03M2 and sulfato groups are groups of the formula -OS03M , in which M is defined as above.
SUBSTITUTE SHEET (R ULE 26) The dye, respectively dyes, of the general formula (1 ) are present in the mixtures in an amount of from 70 to 95% by weight, preferably of from 75 to 90 % by weight, and the dye, respectively dyes of the general formula (2) are present in the mixtures in an s amount of from 5 to 30% by weight, preferably of from 10 to 25 % by weight.
The dye mixtures of the invention may optionally contain one, two or three dyestuffs corresponding to the general formula (3a) or (3b) or both R~
\ N=N
Y~ - S02 z R M03; M
(3 a) Y2 - SOZ \ N N / \
,/
Ra \ ( /
(3b) in which R', R2, R3, R4, M, Y' and Y2 are defined as above. These two monoazo is dyestuffs may be already formed during the synthesis of the disazo dye of formula (1 ) when coupling reactions of the starting compounds are incomplete.
If the dye mixture of the instant invention contains, as a further component, a monoazo dyestuff of formula (3a) or of formula (3b) or both, the dye or dyes of 2o formula (3a) or of formula (3b) or of both are present in the dye mixture of the dyes of formula (1 ) and (2) in the range of 0.01 to 8 % by weight, calculated on the 100 dye mixture of the dyes (1 ) and (2).
The dyes of the general formulae (1 ), (2), (3a) and (3b), in particular if those 2s corresponding to the same general formula have the same chromophore, can have, within the meaning of their Y-moiety, structurally different fiber-reactive groups SUBSTITUTE SHEET (RULE 26) corresponding to their -SOz-Y-moiety. In particular, the dye mixture can contain dyes of the same chromophore conforming to the formula (1 ) and/or dyes of the same chromophore conforming to formula (2), optionally likewise of the general formula (3a) or (3b) or both in which the fiber-reactive groups of the corresponding s -SOz-Y-moiety are partly vinylsulfonyl groups and partly groups in which the Y-moiety is a ~i-ethyl substituted group as defined above, such as f3-chloroethylsufonyl, f5-thiosulfatoethylsulfonyl or, preferably, f3-sulfatoethylsulfonyl groups. If the dye mixtures contain the respective dye components in the form of a vinylsulfonyl dye, the proportion of the respective vinylsulfonyl dye to the respective io dye with a Y-moiety being a ~3-ethyl substituted group as defined above, such as a (3-chloro- or f3-thiosulfato- or f3-sulfatoethyl-sulfonyl dye, will be up to about 30 mol-%, based on the respective dye chromophore. Preference is here given to the dye mixtures in which the proportion of vinylsulfonyl dye to said ~3-substituted ethylsulfonyl dye, such as f3-sulfatoethylsulfonyl dye, is in terms of the molar ratio is between 2 : 98 and 30 : 70.
Radicals of the formulae (4), (5) and (6) R~ s Y~.OzS . v ~ Y~02S
(4) ( 5 ) Rz Ra (Y4 SOz) ~D~*
R/s in the dyes of formulae (1), (2) for n=1, (3a) and (3b) are, for example, 2s 2-(~3-sulfatoethylsulfonyl)phenyl, 3-(~3-sulfatoethylsulfonyl)phenyl, 3- or 4-vinylsulfonylphenyl, 4-(~3-sulfatoethylsulfonyl)phenyl, 2-carboxy-5-(~3-sulfatoethylsulfonyl)phenyl, 4-methoxy-3-(~3-sulfatoethylsulfonyl)-phenyl, 2-ethoxy-4- or -5-(~3-sulfatoethylsulfonyl)phenyl, 2-methyl-4-((3-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5- or -4-(~3-sulfatoethylsulfonyl)phenyl, 2,4-diethoxy-5-((3-sulfato-SUBSTITUTE SHEET (RULE 26) ethylsulfonyl)phenyl, 2,4-dimethoxy-5-(~3-sulfatoethylsulfonyl)phenyl, 2,5-dimethoxy-4-(~-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-(~i-sulfatoethyl-sulfonyl)phenyl, 2- or 3- or 4-(~3-thiosulfatoethylsulfonyl)phenyl, 2-methoxy-5-(~3-thio-sulfatoethylsulfonyl)phenyl, 2-sulfo-4-(~3-phosphatoethylsulfonyl)phenyl, 2-sulfo-4-s vinylsulfonylphenyl and 3- or 4-(~3-acetoxyethylsulfonyl)phenyl and their corresponding vinylsulfonyl derivatives.
Radicals of the formula (6) (Ya'SOz) / D-* (6) to Rs for n=0 in the dyes of formula (2) are, for example 4-methyl-2-sulfophenyl, 4-methoxy-2-sulfophenyl, 4-sulfophenyl, 3-sulfophenyl, 2-sulfophenyl, 4-methoxy-2,5-disulfophenyl, 4-methyl-2,5-disulfophenyl, 1,5-disulfonaphthyl or 1-sulfonaphthyl.
is Preference is given to dye mixtures according to the invention, in which D is the radical of 1,5-disulfonaphthyl R' is methoxy or hydrogen, R2 is hydrogen, 2o R3 is methoxy or hydrogen, R4 is hydrogen, X' is chlorine XZ is the radical 4-(f3-sulfatoethylsulfonyl)phenyl and R', R2, R3 and R4 are in particular preferred each hydrogen and the Y-moieties 2s are each preferable, independently of the other one vinyl or ~i-sulfatoethyl.
The dye mixtures of the 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 fiber-reactive dyes, such as sodium 3o chloride, potassium chloride and sodium sulfate, and also the assistants customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium SUBSTITUTE SHEET (RULE 26) bicarbonate, 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.
If the dye mixtures take the form of dye powders, they contain, as a rule, 10 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 in addition contain the abovementioned buffer substances in a total io amount of up to 5 %, based on the dye powder. If the dye mixtures of the invention are present in aqueous solution, the total dye content of these aqueous solutions is up to about 50 % by weight, the electrolyte salt content of these aqueous solutions preferably being below 10 % by weight, based on the aqueous solutions (liquid preparations) can in general contain the abovementioned buffer substances in an is amount of up to 5 % by weight, preferably up to 2 % by weight.
The dye mixtures of the invention are preparable in a conventional manner, as by mechanically mixing the individual dyes in the necessary proportions, whether in the form of their dye powders or granules or their synthesis solution or of aqueous solutions of the individual dyes in general, which may still include customary 2o auxiliaries.
The dyes according to the general formula (1 ) are known from the U.S. Patents Nos.
2,657,205, 3,387,914, 4,072,463 and 4,257,770 or from one of the above-mentioned publications, and the dyes of the general formula (2) are known from the 2s European Patent Application EP-A 534 342 and from the European Patent Application EP A 177 449.
The dye mixtures of the instant invention are well suitable for dyeing (which includes printing) hydroxy- andlor carboxamido-containing fiber materials by the application and fixing methods numerously described in the art for fiber-reactive dyes, in deep 3o navy shades with good color build-up and good wash-off in respect of unfixed dye portions.
SUBSTITUTE SHEET (RULE 26) The present invention therefore also provides for use of the novel dye mixtures for dyeing (including printing) hydroxy- and/or carboxamido-containing fiber materials and processes for dyeing such fiber materials and processes for dyeing such materials using a dye mixture according to the invention by applying the dye mixture to the substrate in dissolved form and fixing the dyes on the fiber 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 io regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton but also other natural vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose.
is Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11, and nylon-4.
Furthermore, the dye mixtures of the invention can also be used for the fiber-reactive dyeing of wool. Moreover, wool which has been given a nonfelting or low-felting 2o finish (cf. H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd Edition (1972), p.
295-299, especially the finish by the so-called Hercosett process (p. 298); J.
Soc.
Dyers and Colourists 1972, 93-99, and 1975, 33-44) can be dyed with very good fastness properties.
2s The process of dyeing on wool is here carried out in a conventional manner from an acidic medium. For instance, acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH. To obtain a dyeing of acceptable levelness, it is advisable to add a customary leveling agent, for example on the basis of a reaction product of cyanuric so chloride with 3 times the molar amount of an aminobenzenesulfonic acid and/or of an aminonaphthalenesulfonic acid or on the basis of a reaction product of for example stearylamine with ethylene oxide. For instance, the dye mixture of the invention is SUBSTITUTE SHEET (RULE 26) preferably subjected to the exhaustion process initially from an acidic dyebath having a pH of about 3.5 to 5.5 under pH control and the pH is then, toward the end of the dyeing time, shifted into the neutral and perhaps weakly alkaline range up to a pH of 8.5 to bring about, especially for very deep dyeings, the full reactive bond between the dyes of the dye mixtures of the invention and the fiber. At the same time, the dye portion not reactively bound is removed.
The procedure described herein also applies to the production of dyeings on fiber materials composed of other natural polyamides or of synthetic polyamides and io polyurethanes. In general, the material to be dyed is introduced into the bath at a temperature of about 40°C, agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98°C.
However, the dyeings can also be carried out at the boil or in sealed dyeing apparatus at is temperatures of up to 106°C. Since the water solubility of the dye mixtures of the invention is very good, they can also be used with advantage in customary continuous dyeing processes. The color strength of the dye mixtures of the invention is very high.
2o Application of the dye mixtures of the invention is by generally known processes for dyeing and printing fiber materials by the known application techniques for fiber-reactive dyes. Since the dyes of the dye mixtures according to the invention are highly compatible with one another, the dye mixtures of the invention are also advantageously useful in exhaust dyeing processes. Applied in this way for example 2s to cellulose fibers from a long liquor ratio at temperatures between 40 and 105°C, optionally at temperatures up to 130°C, under superatmospheric pressure, and optionally in the presence of customary dyeing assistants with the use of acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, they produce dyeings in very good color yields with excellent color build-up 3o and consistent shade. One possible procedure is to introduce the material into the warm bath, gradually heat the bath to the desired dyeing temperature, and complete the dyeing process at that temperature. The neutral salts which speed up the SUBSTITUTE SHEET (RULE 26) exhaustion of the dyes can also if desired not be added to the bath until the actual dyeing temperature has been reached.
Similarly, the conventional printing processes for cellulose fibers, which can either be s 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 from 100 to 103°C, 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 to alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquour and subsequent hatching 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 Is 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 120 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 160°C.
2o 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 2s compounds. These acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate and disodium hydrogenphosphate.
Treating the dyes of the dye mixtures according to the invention with the acid-binding 3o agents with or without heating bonds the dyes chemically to the cellulose fiber;
especially the dyeings on cellulose, after they have been given the usual aftertreatment of rinsing to remove unfixed dye portions, show excellent wet fastness SUBSTITUTE SHEET (RULE 26) properties, in particular since the unfixed dye portions are readily washed off because of their good cold water solubility.
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 assistants, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic to 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.
is However, the dyeings can also be carried out at the boil or at temperatures up to 120°C (under superatmospheric pressure).
The Examples which follow illustrate the invention. Parts and precentages are by weight, unless otherwise stated. The parts by weight bear the same relation to parts 2o by volume as the kilogram to the liter.
SUBSTITUTE SHEET (RULE 26) Example 1 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) H03SOCHZCH202S (A) \ I OH NHZ
N=N / \ N=N
I
H03S \ / S03H
with 33.3 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) is I (B) HN \
N i 'N
OH HN~N~CI
%Y\
\ t /
with 10 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C) / SOZCH2CHzOS03H
OH NHZ
N=N \
/ \ (C
I
H03S \ / S03H
3o The resulting mixture contains 75% (w/w) of dye (A) and 20% (w/w) of dye (B) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
SUBSTITUTE SHEET (RULE 26) Example 2 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 33.3 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) with 5.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 77.5% (w/w) of dye (A) and 20% (w/w) of dye (B) and 2.5%
(w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent to dyestuff properties (i.e. lightfastness and washfastness).
Example 3 A dye mixture according to the invention is prepared by mechanically mixing is parts of a navy-blue electrolyte-salt containing powder with a content of 50% of a dye of formula (A) with 25 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (B) and 5% (w/w) of dye (C) and dyes 2o wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
lightfastness and washfastness).
Example 4 2s A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 16.6 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting 3o mixture contains 85% (w/w) of dye (A) and 10% (w/w) of dye (B) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness~.
SUBSTITUTE SHEET (RULE 26) Example 5 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 16.6 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C) with 20.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (D).
The resulting mixture contains 75% (w/w) of dye (A) and 10% (w/w) of dye (B) and l0 5% (w/w) of dye (C) and 10% (w/w) of dye (D) and dyes wool in navy-blue shades.
The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
/ SOZCHZCHzOS03H
(D) HN \
is H03SOCHzCH20zS N i _N
I \ OH HN~N~CI
N-N / I \
H03S \ / S03H
2o Example 6 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 16.6 parts of a red electrolyte-salt containing powder with a 2s content of 60% of a dye of formula (B) and with 20.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (D). The resulting mixture contains 80% (wlw) of dye (A) and 10% (w/w) of dye (B) and 10% (w/w) of dye (D) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
Example 7 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye SUBSTITUTE SHEET (RULE 26) of formula (A) with 28.5 parts of a red electrolyte-salt containing powder with a content of 70% of a dye of formula (E) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 75% (w/w) of dye (A) and 20% (w/w) of dye (E) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
(E) / I
H~ \ SOzCH2CH20S03H
l0 S03H
N~ N
\ \ 1' l I / / OH HN'\\N/\CI
N-N / I \
H03S \ / S03H
is Example 8 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 21.5 parts of a red electrolyte-salt containing powder with a 2o content of 70% of a dye of formula (E) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (E) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
Example 9 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 23 parts of a red electrolyte-salt containing powder with a content of 65% of a dye of formula (F) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (F) and 5% (w/w) of dye (C) and dyes SUBSTITUTE SHEET (RULE 26) wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
lightfastness and washfastness).
O
c~
N
N i 'N
\ \ ~ ~ (F) OH HN N F
/ / N=N
/ ( \
H03S \ / S03H
Example 10 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye is of formula (A) with 23 parts of a red electrolyte-salt containing powder with a content of 65% of a dye of formula (F). The resulting mixture contains 85% (w/w) of dye (A) and 15% (w/w) of dye (F) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
2o Example 11 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 30.7 parts of a red electrolyte-salt containing powder with a 2s content of 65% of a dye of formula (G) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 75% (w/w) of dye (A) and 20% (w/w) of dye (G) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
(G) N ~ N / SOZCH2CHZOS03H
\ \
OH HN N N
/ / N=N H
_ \ / __ __ SUBSTITUTE SHEET (RULE 26) Example 12 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 23 parts of a red electrolyte-salt containing powder with a content of 65% of a dye of formula (G) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (G) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
to lightfastness and washfastness).
Example 13 is A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 30 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (H) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 20 80% (w/w) of dye (A) and 15% (w/w) of dye (H) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
lightfastness and washfastness).
2s CI (H) N i 'N / SO2CH2CHZOS03H
HsC O \
OH HN N N
/ N-N H
3o S03H
H03S \ / S03H
SUBSTITUTE SHEET (RULE 26) Example 14 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 30 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (I) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (I) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
to lightfastness and washfastness).
NHCN
N i _N / S02CH2CH20S03H
H3C'O \ ~ ~ \ I
is I / OH HN N H
N=N / I \
H03S \ / S03H
Example 15 2o A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 30 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (J) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 2s 80% (w/w) of dye (A) and 15% (w/w) of dye (J) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
lightfastness and washfastness).
(J) NHCN
30 ~ S02CH2CH20S03H
N~N
HsC \
OH HN N N
N-N H
I\
H03S ~ ~ S03H
SUBSTITUTE SHEET (RULE 26)
io Navy-dyeing mixtures of fiber-reactive dyes are known from European Patent Applications EP-A 0588257, EP-A 0668328, EP-A 0127456. However these dye mixtures have still some deficiencies, such as, for ex., when applied to substrates other than cellulose, for example wool. Deep navy shades on carboxamido is containing fibers are usually achieved by the application of mordant dyes.
Mordant dyes are well known for their good fastness - and dyeing properties. However they have ecological disadvantages, so that alternative reactive dye mixtures are desirable.
2o With the present invention, deep navy-dyeing reactive dye mixtures have been found which unexpectedly and surprisingly have improved properties, such as improved resistance to ammonium aftertreatment and levelness in regard to the dyeing of wool. The present invention discloses dye mixtures comprising one or more, such as one, two or three, disazo dyes conforming to the general formula (1 ) R~ R3 Y~ - 02S \ N = N / I \ N = N I S02 - Y2 R ~ MO3S \ ~ SO3M R4 (1 ) one or more, such as one, two, three or four, monoazo dyes conforming to the general formula (2), SUBSTITUTE SHEET (R ULE 26) X~
i~ ~N
(Ya'SOZ)n D~N ~N~Xz Rs~ O H H N
(2) M03S ~ ~ S03M
in which:
R' is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably s methoxy or hydrogen and in particular hydrogen;
R2 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably hydrogen;
R3 has one of the meanings of R1 R4 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably io hydrogen;
R5 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy, sulfo or hydrogen and in particular sulfo;
R6 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy, sulfo or hydrogen and in particular sulfo;
is D is a benzene or naphthalene radical;
n is0or1 X' is a fluoro, chloro, cyanamido, or morpholino group or a group of the following formulae; NR7R$ or OR9 or wherein R»
zo *~
N SOZ Ys Rio R' is hydrogen, methyl, ethyl, hydroxyethyl, methoxyethyl, ethoxyethyl, or 2s sulfoethyl, preferably ethyl, methoxyethyl, sulfoethyl SUBSTITUTE SHEET (RULE 26) R8 has one of the meanings of R';
R9 has one of the meanings of R7;
R' has one of the meanings of R';
R" is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably s methoxy or hydrogen and in particular hydrogen;
R'2 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy or hydrogen and in particular hydrogen;
X2 has one of the meanings of X';
Y' is vinyl, or is ethyl substituted in the ~i-position by a substituent which is io eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphato, sulfobenzoyloxy and p-toluylsulfonyloxy, and Y' is preferably vinyl, f3-chloroethyl, f3-thiosulfatoethyl or f3-sulfatoethyl and is in particular preferably vinyl or ~i-sulfatoethyl;
is Y2 has one of the meanings of Y';
Y3 has one of the meanings of Y';
Y4 has one of the meanings of Y';
M denotes hydrogen or an alkali metal such as lithium, sodium and potassium.
Both in the formulae mentioned above and in those below, the individual formula members, both with different and with the same designation within a formula or the various formulae, can within the scope of their definitions have meanings which are the same as or different from one another.
The groups "sulfo", "thiosulfato", "carboxy", "phosphato" and "sulfato"
include both the acid form and the salt form of these groups. Accordingly, sulfo groups are groups of the formula -S03M' , thiosulfato groups are groups of the formula -S-S03M , carboxy groups are groups of the formula -COOM , phosphato groups are groups of the formula -OP03M2 and sulfato groups are groups of the formula -OS03M , in which M is defined as above.
SUBSTITUTE SHEET (R ULE 26) The dye, respectively dyes, of the general formula (1 ) are present in the mixtures in an amount of from 70 to 95% by weight, preferably of from 75 to 90 % by weight, and the dye, respectively dyes of the general formula (2) are present in the mixtures in an s amount of from 5 to 30% by weight, preferably of from 10 to 25 % by weight.
The dye mixtures of the invention may optionally contain one, two or three dyestuffs corresponding to the general formula (3a) or (3b) or both R~
\ N=N
Y~ - S02 z R M03; M
(3 a) Y2 - SOZ \ N N / \
,/
Ra \ ( /
(3b) in which R', R2, R3, R4, M, Y' and Y2 are defined as above. These two monoazo is dyestuffs may be already formed during the synthesis of the disazo dye of formula (1 ) when coupling reactions of the starting compounds are incomplete.
If the dye mixture of the instant invention contains, as a further component, a monoazo dyestuff of formula (3a) or of formula (3b) or both, the dye or dyes of 2o formula (3a) or of formula (3b) or of both are present in the dye mixture of the dyes of formula (1 ) and (2) in the range of 0.01 to 8 % by weight, calculated on the 100 dye mixture of the dyes (1 ) and (2).
The dyes of the general formulae (1 ), (2), (3a) and (3b), in particular if those 2s corresponding to the same general formula have the same chromophore, can have, within the meaning of their Y-moiety, structurally different fiber-reactive groups SUBSTITUTE SHEET (RULE 26) corresponding to their -SOz-Y-moiety. In particular, the dye mixture can contain dyes of the same chromophore conforming to the formula (1 ) and/or dyes of the same chromophore conforming to formula (2), optionally likewise of the general formula (3a) or (3b) or both in which the fiber-reactive groups of the corresponding s -SOz-Y-moiety are partly vinylsulfonyl groups and partly groups in which the Y-moiety is a ~i-ethyl substituted group as defined above, such as f3-chloroethylsufonyl, f5-thiosulfatoethylsulfonyl or, preferably, f3-sulfatoethylsulfonyl groups. If the dye mixtures contain the respective dye components in the form of a vinylsulfonyl dye, the proportion of the respective vinylsulfonyl dye to the respective io dye with a Y-moiety being a ~3-ethyl substituted group as defined above, such as a (3-chloro- or f3-thiosulfato- or f3-sulfatoethyl-sulfonyl dye, will be up to about 30 mol-%, based on the respective dye chromophore. Preference is here given to the dye mixtures in which the proportion of vinylsulfonyl dye to said ~3-substituted ethylsulfonyl dye, such as f3-sulfatoethylsulfonyl dye, is in terms of the molar ratio is between 2 : 98 and 30 : 70.
Radicals of the formulae (4), (5) and (6) R~ s Y~.OzS . v ~ Y~02S
(4) ( 5 ) Rz Ra (Y4 SOz) ~D~*
R/s in the dyes of formulae (1), (2) for n=1, (3a) and (3b) are, for example, 2s 2-(~3-sulfatoethylsulfonyl)phenyl, 3-(~3-sulfatoethylsulfonyl)phenyl, 3- or 4-vinylsulfonylphenyl, 4-(~3-sulfatoethylsulfonyl)phenyl, 2-carboxy-5-(~3-sulfatoethylsulfonyl)phenyl, 4-methoxy-3-(~3-sulfatoethylsulfonyl)-phenyl, 2-ethoxy-4- or -5-(~3-sulfatoethylsulfonyl)phenyl, 2-methyl-4-((3-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5- or -4-(~3-sulfatoethylsulfonyl)phenyl, 2,4-diethoxy-5-((3-sulfato-SUBSTITUTE SHEET (RULE 26) ethylsulfonyl)phenyl, 2,4-dimethoxy-5-(~3-sulfatoethylsulfonyl)phenyl, 2,5-dimethoxy-4-(~-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-(~i-sulfatoethyl-sulfonyl)phenyl, 2- or 3- or 4-(~3-thiosulfatoethylsulfonyl)phenyl, 2-methoxy-5-(~3-thio-sulfatoethylsulfonyl)phenyl, 2-sulfo-4-(~3-phosphatoethylsulfonyl)phenyl, 2-sulfo-4-s vinylsulfonylphenyl and 3- or 4-(~3-acetoxyethylsulfonyl)phenyl and their corresponding vinylsulfonyl derivatives.
Radicals of the formula (6) (Ya'SOz) / D-* (6) to Rs for n=0 in the dyes of formula (2) are, for example 4-methyl-2-sulfophenyl, 4-methoxy-2-sulfophenyl, 4-sulfophenyl, 3-sulfophenyl, 2-sulfophenyl, 4-methoxy-2,5-disulfophenyl, 4-methyl-2,5-disulfophenyl, 1,5-disulfonaphthyl or 1-sulfonaphthyl.
is Preference is given to dye mixtures according to the invention, in which D is the radical of 1,5-disulfonaphthyl R' is methoxy or hydrogen, R2 is hydrogen, 2o R3 is methoxy or hydrogen, R4 is hydrogen, X' is chlorine XZ is the radical 4-(f3-sulfatoethylsulfonyl)phenyl and R', R2, R3 and R4 are in particular preferred each hydrogen and the Y-moieties 2s are each preferable, independently of the other one vinyl or ~i-sulfatoethyl.
The dye mixtures of the 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 fiber-reactive dyes, such as sodium 3o chloride, potassium chloride and sodium sulfate, and also the assistants customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium SUBSTITUTE SHEET (RULE 26) bicarbonate, 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.
If the dye mixtures take the form of dye powders, they contain, as a rule, 10 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 in addition contain the abovementioned buffer substances in a total io amount of up to 5 %, based on the dye powder. If the dye mixtures of the invention are present in aqueous solution, the total dye content of these aqueous solutions is up to about 50 % by weight, the electrolyte salt content of these aqueous solutions preferably being below 10 % by weight, based on the aqueous solutions (liquid preparations) can in general contain the abovementioned buffer substances in an is amount of up to 5 % by weight, preferably up to 2 % by weight.
The dye mixtures of the invention are preparable in a conventional manner, as by mechanically mixing the individual dyes in the necessary proportions, whether in the form of their dye powders or granules or their synthesis solution or of aqueous solutions of the individual dyes in general, which may still include customary 2o auxiliaries.
The dyes according to the general formula (1 ) are known from the U.S. Patents Nos.
2,657,205, 3,387,914, 4,072,463 and 4,257,770 or from one of the above-mentioned publications, and the dyes of the general formula (2) are known from the 2s European Patent Application EP-A 534 342 and from the European Patent Application EP A 177 449.
The dye mixtures of the instant invention are well suitable for dyeing (which includes printing) hydroxy- andlor carboxamido-containing fiber materials by the application and fixing methods numerously described in the art for fiber-reactive dyes, in deep 3o navy shades with good color build-up and good wash-off in respect of unfixed dye portions.
SUBSTITUTE SHEET (RULE 26) The present invention therefore also provides for use of the novel dye mixtures for dyeing (including printing) hydroxy- and/or carboxamido-containing fiber materials and processes for dyeing such fiber materials and processes for dyeing such materials using a dye mixture according to the invention by applying the dye mixture to the substrate in dissolved form and fixing the dyes on the fiber 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 io regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton but also other natural vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose.
is Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11, and nylon-4.
Furthermore, the dye mixtures of the invention can also be used for the fiber-reactive dyeing of wool. Moreover, wool which has been given a nonfelting or low-felting 2o finish (cf. H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd Edition (1972), p.
295-299, especially the finish by the so-called Hercosett process (p. 298); J.
Soc.
Dyers and Colourists 1972, 93-99, and 1975, 33-44) can be dyed with very good fastness properties.
2s The process of dyeing on wool is here carried out in a conventional manner from an acidic medium. For instance, acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH. To obtain a dyeing of acceptable levelness, it is advisable to add a customary leveling agent, for example on the basis of a reaction product of cyanuric so chloride with 3 times the molar amount of an aminobenzenesulfonic acid and/or of an aminonaphthalenesulfonic acid or on the basis of a reaction product of for example stearylamine with ethylene oxide. For instance, the dye mixture of the invention is SUBSTITUTE SHEET (RULE 26) preferably subjected to the exhaustion process initially from an acidic dyebath having a pH of about 3.5 to 5.5 under pH control and the pH is then, toward the end of the dyeing time, shifted into the neutral and perhaps weakly alkaline range up to a pH of 8.5 to bring about, especially for very deep dyeings, the full reactive bond between the dyes of the dye mixtures of the invention and the fiber. At the same time, the dye portion not reactively bound is removed.
The procedure described herein also applies to the production of dyeings on fiber materials composed of other natural polyamides or of synthetic polyamides and io polyurethanes. In general, the material to be dyed is introduced into the bath at a temperature of about 40°C, agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98°C.
However, the dyeings can also be carried out at the boil or in sealed dyeing apparatus at is temperatures of up to 106°C. Since the water solubility of the dye mixtures of the invention is very good, they can also be used with advantage in customary continuous dyeing processes. The color strength of the dye mixtures of the invention is very high.
2o Application of the dye mixtures of the invention is by generally known processes for dyeing and printing fiber materials by the known application techniques for fiber-reactive dyes. Since the dyes of the dye mixtures according to the invention are highly compatible with one another, the dye mixtures of the invention are also advantageously useful in exhaust dyeing processes. Applied in this way for example 2s to cellulose fibers from a long liquor ratio at temperatures between 40 and 105°C, optionally at temperatures up to 130°C, under superatmospheric pressure, and optionally in the presence of customary dyeing assistants with the use of acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, they produce dyeings in very good color yields with excellent color build-up 3o and consistent shade. One possible procedure is to introduce the material into the warm bath, gradually heat the bath to the desired dyeing temperature, and complete the dyeing process at that temperature. The neutral salts which speed up the SUBSTITUTE SHEET (RULE 26) exhaustion of the dyes can also if desired not be added to the bath until the actual dyeing temperature has been reached.
Similarly, the conventional printing processes for cellulose fibers, which can either be s 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 from 100 to 103°C, 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 to alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquour and subsequent hatching 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 Is 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 120 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 160°C.
2o 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 2s compounds. These acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate and disodium hydrogenphosphate.
Treating the dyes of the dye mixtures according to the invention with the acid-binding 3o agents with or without heating bonds the dyes chemically to the cellulose fiber;
especially the dyeings on cellulose, after they have been given the usual aftertreatment of rinsing to remove unfixed dye portions, show excellent wet fastness SUBSTITUTE SHEET (RULE 26) properties, in particular since the unfixed dye portions are readily washed off because of their good cold water solubility.
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 assistants, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic to 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.
is However, the dyeings can also be carried out at the boil or at temperatures up to 120°C (under superatmospheric pressure).
The Examples which follow illustrate the invention. Parts and precentages are by weight, unless otherwise stated. The parts by weight bear the same relation to parts 2o by volume as the kilogram to the liter.
SUBSTITUTE SHEET (RULE 26) Example 1 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) H03SOCHZCH202S (A) \ I OH NHZ
N=N / \ N=N
I
H03S \ / S03H
with 33.3 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) is I (B) HN \
N i 'N
OH HN~N~CI
%Y\
\ t /
with 10 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C) / SOZCH2CHzOS03H
OH NHZ
N=N \
/ \ (C
I
H03S \ / S03H
3o The resulting mixture contains 75% (w/w) of dye (A) and 20% (w/w) of dye (B) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
SUBSTITUTE SHEET (RULE 26) Example 2 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 33.3 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) with 5.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 77.5% (w/w) of dye (A) and 20% (w/w) of dye (B) and 2.5%
(w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent to dyestuff properties (i.e. lightfastness and washfastness).
Example 3 A dye mixture according to the invention is prepared by mechanically mixing is parts of a navy-blue electrolyte-salt containing powder with a content of 50% of a dye of formula (A) with 25 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (B) and 5% (w/w) of dye (C) and dyes 2o wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
lightfastness and washfastness).
Example 4 2s A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 16.6 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting 3o mixture contains 85% (w/w) of dye (A) and 10% (w/w) of dye (B) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness~.
SUBSTITUTE SHEET (RULE 26) Example 5 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 16.6 parts of a red electrolyte-salt containing powder with a content of 60% of a dye of formula (B) with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C) with 20.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (D).
The resulting mixture contains 75% (w/w) of dye (A) and 10% (w/w) of dye (B) and l0 5% (w/w) of dye (C) and 10% (w/w) of dye (D) and dyes wool in navy-blue shades.
The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
/ SOZCHZCHzOS03H
(D) HN \
is H03SOCHzCH20zS N i _N
I \ OH HN~N~CI
N-N / I \
H03S \ / S03H
2o Example 6 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 16.6 parts of a red electrolyte-salt containing powder with a 2s content of 60% of a dye of formula (B) and with 20.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (D). The resulting mixture contains 80% (wlw) of dye (A) and 10% (w/w) of dye (B) and 10% (w/w) of dye (D) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
Example 7 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye SUBSTITUTE SHEET (RULE 26) of formula (A) with 28.5 parts of a red electrolyte-salt containing powder with a content of 70% of a dye of formula (E) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 75% (w/w) of dye (A) and 20% (w/w) of dye (E) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
(E) / I
H~ \ SOzCH2CH20S03H
l0 S03H
N~ N
\ \ 1' l I / / OH HN'\\N/\CI
N-N / I \
H03S \ / S03H
is Example 8 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 21.5 parts of a red electrolyte-salt containing powder with a 2o content of 70% of a dye of formula (E) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (E) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
Example 9 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 23 parts of a red electrolyte-salt containing powder with a content of 65% of a dye of formula (F) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (F) and 5% (w/w) of dye (C) and dyes SUBSTITUTE SHEET (RULE 26) wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
lightfastness and washfastness).
O
c~
N
N i 'N
\ \ ~ ~ (F) OH HN N F
/ / N=N
/ ( \
H03S \ / S03H
Example 10 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye is of formula (A) with 23 parts of a red electrolyte-salt containing powder with a content of 65% of a dye of formula (F). The resulting mixture contains 85% (w/w) of dye (A) and 15% (w/w) of dye (F) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
2o Example 11 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 30.7 parts of a red electrolyte-salt containing powder with a 2s content of 65% of a dye of formula (G) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 75% (w/w) of dye (A) and 20% (w/w) of dye (G) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
(G) N ~ N / SOZCH2CHZOS03H
\ \
OH HN N N
/ / N=N H
_ \ / __ __ SUBSTITUTE SHEET (RULE 26) Example 12 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 23 parts of a red electrolyte-salt containing powder with a content of 65% of a dye of formula (G) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (G) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
to lightfastness and washfastness).
Example 13 is A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 30 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (H) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 20 80% (w/w) of dye (A) and 15% (w/w) of dye (H) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
lightfastness and washfastness).
2s CI (H) N i 'N / SO2CH2CHZOS03H
HsC O \
OH HN N N
/ N-N H
3o S03H
H03S \ / S03H
SUBSTITUTE SHEET (RULE 26) Example 14 A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 30 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (I) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (I) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
to lightfastness and washfastness).
NHCN
N i _N / S02CH2CH20S03H
H3C'O \ ~ ~ \ I
is I / OH HN N H
N=N / I \
H03S \ / S03H
Example 15 2o A dye mixture according to the invention is prepared by mechanically mixing parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye of formula (A) with 30 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (J) and with 10.0 parts of a red electrolyte-salt containing powder with a content of 50% of a dye of formula (C). The resulting mixture contains 2s 80% (w/w) of dye (A) and 15% (w/w) of dye (J) and 5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent dyestuff properties (i.e.
lightfastness and washfastness).
(J) NHCN
30 ~ S02CH2CH20S03H
N~N
HsC \
OH HN N N
N-N H
I\
H03S ~ ~ S03H
SUBSTITUTE SHEET (RULE 26)
Claims (6)
1. A dye mixture comprising one or more, such as one, two or three, disazo dyes conforming to the general formula (1) one or more, such as one, two, three or four, monoazo dyes conforming to the general formula (2) in which:
R1 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R2 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R3 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R4 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R5 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R6 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy D is a benzene or naphthalene radical;
X1 is a fluoro, chloro, cyanamido, or morpholino group or a group of the following formulae; NR7R8 or OR9 or wherein R7 is hydrogen, C1-C4 alkyl, or C1-C4 alkyl which is substituted by an alkoxy, hydroxy or sulfo group;
R8 has one of the meanings of R7;
R9 has one of the meanings of R7;
R10 has one of the meanings of R7;
R10 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R12 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy X2 has one of the meanings of X1;
Y1 is vinyl, or is ethyl substituted in the .beta.-position by a substituent which is eliminated by the action of an alkali, forming the vinyl group;
Y2 has one of the meanings of Y1;
Y3 has one of the meanings of Y1;
Y4 has one of the meanings of Y1;
M denotes hydrogen or an alkali metal, such as litihium, sodium and potassium.
R1 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R2 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R3 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R4 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R5 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R6 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy D is a benzene or naphthalene radical;
X1 is a fluoro, chloro, cyanamido, or morpholino group or a group of the following formulae; NR7R8 or OR9 or wherein R7 is hydrogen, C1-C4 alkyl, or C1-C4 alkyl which is substituted by an alkoxy, hydroxy or sulfo group;
R8 has one of the meanings of R7;
R9 has one of the meanings of R7;
R10 has one of the meanings of R7;
R10 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy R12 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy X2 has one of the meanings of X1;
Y1 is vinyl, or is ethyl substituted in the .beta.-position by a substituent which is eliminated by the action of an alkali, forming the vinyl group;
Y2 has one of the meanings of Y1;
Y3 has one of the meanings of Y1;
Y4 has one of the meanings of Y1;
M denotes hydrogen or an alkali metal, such as litihium, sodium and potassium.
2. The dye mixture of claim 1, comprising one or more dyestuffs of the formula (1) in a mixing ratio of 70 to 95% by weight and one or more dyestuffs of the formula (2) in a mixing ratio of 5 to 30% by weight.
3. The dye mixture of claim 1, comprising one or more dyestuffs of the formula (1) in a mixing ratio of 75 to 90 % and one or more dyestuffs of the formula (2) in a mixing ratio of 10 to 25 % by weight.
4. The dye mixture of claim 1, comprising one or more dyestuffs of the formula (1) in a mixing ratio of 75-90 % weight and one or more dyestuffs of the formula (2) in a mixing ratio of 8-15 % by weight and one or more dyestuffs of the formula (3a) and (3b) in a mixing ratio of 2-10 % by weight in which R1, R2, R3, R4, M, Y1 and Y2 are defined as in Claim 1.
5. A method for the preparation of the inventive dye mixtures in a conventional manner by mechanically mixing the individual dyes in the necessary proportions.
6. A process for dyeing hydroxy- and/or carboxamido-containing fiber material, in which dyes 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 employing as dyes a dye mixture as claimed and defined in claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29196199A | 1999-04-15 | 1999-04-15 | |
| US09/291,961 | 1999-04-15 | ||
| PCT/EP2000/003150 WO2000063298A1 (en) | 1999-04-15 | 2000-04-08 | Deep navy dye mixtures of fiber-reactive azo dyes and a method for their preparation and a process for dyeing hydroxy and/or carboxamido containing fibers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2370403A1 true CA2370403A1 (en) | 2000-10-26 |
Family
ID=23122603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002370403A Abandoned CA2370403A1 (en) | 1999-04-15 | 2000-04-08 | Deep navy dye mixtures of fiber-reactive azo dyes and a method for their preparation and a process for dyeing hydroxy and/or carboxamido containing fibers |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1173522A1 (en) |
| JP (1) | JP2002542366A (en) |
| KR (1) | KR20020033090A (en) |
| CN (1) | CN1344294A (en) |
| AU (1) | AU4294600A (en) |
| BR (1) | BR0009692A (en) |
| CA (1) | CA2370403A1 (en) |
| MX (1) | MXPA01010432A (en) |
| TR (1) | TR200102952T2 (en) |
| WO (1) | WO2000063298A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4639490B2 (en) * | 2001-02-20 | 2011-02-23 | 住友化学株式会社 | Reactive dye mixtures and their application to textile materials |
| JP4486810B2 (en) | 2003-01-08 | 2010-06-23 | 富士フイルム株式会社 | Coloring composition and inkjet recording method |
| KR20060123177A (en) * | 2003-10-20 | 2006-12-01 | 시바 스페셜티 케미칼스 홀딩 인크. | Mixtures of reactive dyes and their use |
| KR100686978B1 (en) * | 2006-04-21 | 2007-02-26 | (주)경인양행 | Composition of reactive dyestuffs and methods for dyeing fiber using the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02202956A (en) * | 1989-01-24 | 1990-08-13 | Rika Sangyo Kk | Reactive black dye composition |
| DE4414320A1 (en) * | 1994-04-25 | 1995-10-26 | Hoechst Ag | Black dye mixtures of fiber-reactive azo dyes and their use for dyeing fiber material containing hydroxyl and / or carbonamide groups |
| DE19508156A1 (en) * | 1995-03-08 | 1996-09-12 | Hoechst Ag | Black dye mixtures of fiber-reactive azo dyes and their use for dyeing fiber material containing hydroxyl and / or carbonamide groups |
| DE19511688C2 (en) * | 1995-03-30 | 1999-07-22 | Dystar Textilfarben Gmbh & Co | Dye mixtures of fiber-reactive azo dyes and their use for dyeing fiber material containing hydroxyl and / or carbonamide groups |
| DE19635999A1 (en) * | 1996-09-05 | 1998-03-12 | Dystar Textilfarben Gmbh & Co | Dye mixtures of fiber-reactive azo dyes and their use for dyeing fiber material containing hydroxyl and / or carbonamide groups |
| JPH11335576A (en) * | 1998-05-28 | 1999-12-07 | Sumitomo Chem Co Ltd | Reaction dye composition and dyeing or printing method of fiber material by use thereof |
| TW460545B (en) * | 1998-07-21 | 2001-10-21 | Dystar Textilfarben Gmbh & Amp | Dye mixture |
| US6171349B1 (en) * | 1999-01-20 | 2001-01-09 | Everlight Usa, Inc. | Reactive dye composition |
-
2000
- 2000-04-08 KR KR1020017012980A patent/KR20020033090A/en not_active Application Discontinuation
- 2000-04-08 EP EP00922621A patent/EP1173522A1/en not_active Withdrawn
- 2000-04-08 CN CN00805263A patent/CN1344294A/en active Pending
- 2000-04-08 TR TR2001/02952T patent/TR200102952T2/en unknown
- 2000-04-08 CA CA002370403A patent/CA2370403A1/en not_active Abandoned
- 2000-04-08 JP JP2000612379A patent/JP2002542366A/en active Pending
- 2000-04-08 WO PCT/EP2000/003150 patent/WO2000063298A1/en not_active Application Discontinuation
- 2000-04-08 MX MXPA01010432A patent/MXPA01010432A/en unknown
- 2000-04-08 AU AU42946/00A patent/AU4294600A/en not_active Abandoned
- 2000-04-08 BR BR0009692-0A patent/BR0009692A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| TR200102952T2 (en) | 2002-04-22 |
| WO2000063298A1 (en) | 2000-10-26 |
| CN1344294A (en) | 2002-04-10 |
| AU4294600A (en) | 2000-11-02 |
| BR0009692A (en) | 2002-01-08 |
| KR20020033090A (en) | 2002-05-04 |
| EP1173522A1 (en) | 2002-01-23 |
| MXPA01010432A (en) | 2002-03-27 |
| JP2002542366A (en) | 2002-12-10 |
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