Title of Invention

WATER-SOLUBLE FIBER-REACTIVE DISAZO DYES, AND A PROCESS FOR PREPARING THE SAME"

Abstract The invention relates to dyes of general formula (1), in which R11, R2, M, Z, v and x are defined as cited in claim 1, to the production of the same and to the use of said dyes for colouring or printing material containing hydroxy and/or carbonamide groups, preferably fibrous material. (FIG. 1)
Full Text DESCRIPTION
Water-soluble fiber-reactive disazo dyes, preparation thereof and use thereof
This invention relates to the field of fiber-reactive copper complex disazo dyes.
Copper complexes of fiber-reactive disazo compounds containing one or more fiber-
reactive groups are known for example from DE-B-1 544 541, DE-B-1 644 155,
EP 668 328, DE 32 02 120, EP 085 378, EP 040 806, EP 085 378, EP 203 505,
DE 3941620, DE 4039866, EP 281898, EP 395951. However, they have certain
application defects, for example an excessive dependence of the color yield on
varying parameters in the dyeing process, or an inadequate or unlevel color build-up
on cotton, good color build-up resulting from the ability of a dye to provide a stronger
dyeing when used in a higher dye concentration in the dyebath. Moreover, these
dyes exhibit unsatisfactory fixation yields, i.e., the portion of dye permanently fixed to
the material to be dyed is too low, especially at low temperatures, and also
unsatisfactory wash- and lightfastnesses.
However, it is important, for ecological and economic reasons, to provide dyes
having particularly high fixation yields in order that the portion of unfixed dye in the
dyehouse effluent may be minimized. Moreover, dyes should always provide
uniformly strong dyeings, ideally regardless of changing dyeing parameters, for
example the dyeing temperature in the dyeing process. Furthermore, washfastness
requirements are more stringent these days.
The present invention now provides dyes of the general formula (1) which
surprisingly afford distinctly superior washfastnesses and lightfastnesses coupled
with very good build-up. Moreover, these dyes have higher fixation yields and a
distinctly lower parameter dependence in dyeing. They are therefore also more
compatible with other dyes which fix at distinctly lower temperatures.
The invention accordingly provides dyes of the general formula (1):
where
M is hydrogen, alkali, ammonium or the equivalent of an alkaline earth metal ion
v is 0 or 1 and
Z is-CH=CH2or -CH2CH2Z1,
where
Z1 is hydroxyl or an alkali-detachable group, and
R1 is hydrogen or C1-C4-alkyl;
R2 is a moiety of the general formulae (2), (3), (4) or (5)
where
T1 is hydrogen, methyl, fluorine or chlorine,
T2 is hydrogen, fluorine or chlorine with the proviso that T2 and T1 are not both
hydrogen;
T3 is hydrogen, fluorine or chlorine;
A is C1 to C4-alkyl which may be substituted by up to two substituents selected
from the group consisting of chloro, bromo, hydroxyl and carboxyl, C2 to C4
alkenyl which may be substituted by up to two substituents from the group
consisting of chloro, bromo and hydroxyl, or phenyl,
L is phenylene or naphthalene, which may be substituted by up to two
substituents selected from the group consisting of chloro, bromo, hydroxyl, C
to C4-alkyl especially methyl, ethyl, sulfo and cyano, or else a C2 to C6
alkylene;
Z is-CH=CH2, -CH2CH2Z1,
where
Z1 is hydroxyl or an alkali-detachable group.
(C1-C4)-Alkyl groups A and R1 can be straight-chain or branched and is in particular
selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,
sec-butyl and tert-butyl. Preference is given to methyl and ethyl. Substituted C1 to C4
alkyl groups A are in particular carboxyethyl, carboxypropyl, 1,2-dibromoethyl or
chloromethyl. Substituted alkyl radicals A are preferably 2-bromoethenyl or
2-chloroethenyl.
Examples of preferred R2 radicals of the general formula (2) are: 2,4-difluoro-
pyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoropyrimidin-6-yl, 5-chloro-
4,6-difluoropyrimidin-2-yl, 4,5-difluoropyrimidin-6-yl, 5-chloro-4-fluoropyrimidin-6-yl,
2,4,5-trichloropyrimidin-6-yl, 4,5-dichloropyrimidin-6-yl, 2,4-dichloropyrimidin-6-yl, 4-
fluoropyrimidin-6-yl, 4-chloropyrimidin-6-yl.
Particular preference is given to R2 being 2,4-difluoropyrimidin-6-yl or 5-chloro-2,4-
difluoropyrimidin-6-yl.
An example of a preferred R2 radical of the general formula (3) is
2,3-dichloroquinoxaline-6-carbonyl.
Examples of preferred R2 radicals of the general formula (4) are acetyl, n-propionyl
and n-butyryl; particular preference is given to R2 being acetyl.
Examples of preferred R2 radicals of the general formula (5) are 3-chloroethyl-
sulfonylbenzoyl and 2-chloroethylsulfonylpropionyl.
In the foregoing general formulae and also in the subsequent general formulae, the
individual symbols, whether they bear identical or different designations within any
one general formula, can have meanings under their definition which are mutually
identical or different.
The dyes of the general formula (1) can possess different fiber-reactive groups
-SO2Z within the meaning of Z. Examples of alkali-eliminable substituents Z1 in the ß-
position of the ethyl group of Y or Y" are halogen atoms, such as chlorine and
bromine, ester groups of organic carboxylic and sulfonic acids, such as
alkylcarboxylic acids, optionally substituted benzenecarboxylic acids and optionallyi
substituted benzenesulfonic acids, such as the groups alkanoyloxy of 2 to 5 carbon
atoms, of which in particular acetyloxy, benzoyloxy, sulfobenzoyloxy,
phenylsulfonyloxy and tolylsulfonyloxy, further acidic ester groups of inorganic acids,

as of phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and
thiosulfato groups), similarly dialkylamino groups having alkyl groups of 1 to 4 carbon
atoms each, such as dimethyiamino and diethylamino.
More particularly, the fiber-reactive groups -SO2Z can be first vinylsulfonyl groups
and secondly groups -CH2CH2Z1, preferably ß-thiosulfatoethyl and especially b-
sulfatoethylsulfonyl groups.
The groups sulfo, carboxyl, include not only their acid form but also their salt form.
Accordingly, sulfo groups are groups conforming to the general formula -SO3M,
carboxyl groups .are groups conforming to the general formula -COOM ,in each of
which M is as defined above.
Preference among the diazo compounds of the general formula (1) is given to those
which conform to the general formula (1a)
where M, R1 and R2 are each as defined above.
The dyes of the general formula (1) according to the invention are preparable for |
example by diazotization of a substituted aromatic amine of the general formula (0)
and coupling onto a substituted aminonaphthol of the general formula (7)
and subsequent diazotization of the resulting aminomonoazo dye of the general
formula (8)
and coupling at a pH of 6 to 9, where appropriate in the presence of a dispersant,
onto the terminal coupling component of the general formula (9)
followed by a subsequent coppering reaction with copper sulfate pentahydrate.
Diazotizable amines having complexing radicals of the general formula (6) are for
example 3-amino-4-hydroxy-5-sulfophenyl b-sulfatoethyl sulfone or 3-amino-4-
hydroxy-5-sulfophenyl vinyl sulfone.
Compounds of the general formula (7) are for example 2-amino-5-
hydroxynaphthalene-7-sulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid,
2-amino-5-hydroxynaphthalene-1,7-disulfonic acid and 2-amino-8-
hydroxynaphthalene-3,6-disulfonic acid.
Compounds of the general formula (8) and (9) are for example known from
EP 0 085 378, EP 0 084 849 and can be prepared by common methods.
The separation and isolation, from the aqueous synthesis solutions, of the
compounds of the general formula (1) according to the invention can be effected
according to generally known methods for water-soluble compounds, for example by
precipitating from the reaction medium by means of an electrolyte, such as sodium
chloride or potassium chloride for example, or by evaporating the reaction solution
itself, for example by spray drying. In the latter case, it is frequently advisable first to
precipitate any sulfate in the solutions as calcium sulfate and remove it by filtration.
The dyes of the invention can be present as a preparation in solid or in liquid
(dissolved) form. In solid form, they generally include the electrolyte salts customary
for water-soluble and especially for fiber-reactive dyes, such as sodium chloride,
potassium chloride and sodium sulfate, and may further include the auxiliaries
customary in commercial dyes, such as buffer substances capable of setting a pH in
aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium
bicarbonate, sodium dihydrogenphosphate, sodium tricitrate and disodium hydroien-
phosphate, or small amounts of siccatives; if they are present in a liquid, aqueous;
solution (including the presence of thickeners of the type customary in print pastes),
they may also include substances which ensure a long life for these preparations, for
example mold preventatives.
In general, the dyes of the invention are present as dye powders containing 10 to
80% by weight, based on the dye powder or the preparation, of an electrolyte salt
which is also referred to as a standardizing agent. These dye powders may
additionally include the aforementioned buffer substances in a total amount of up to
10% by weight, based on the dye powder. If the dyes of the invention are present in
aqueous solution, the total dye content of these aqueous solutions will be 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 10% by weight,
based on the aqueous solution; the aqueous solutions (liquid preparations) may
include the aforementioned buffer substances in an amount which is generally up to
10% by weight, preferably up to 2% by weight.
The dyes of the invention have useful application properties. They are used for
dyeing or printing hydroxyl- and/or carboxamido-containing materials, for example in
the form of sheetlike structures, such as paper and leather or of films, for example
composed of polyamide, or in bulk, as for example of polyamide and polyurethane,
but especially for dyeing or printing these materials in fiber form. Similarly, the as-
synthesized solutions of the dyes of the invention, if appropriate after addition of a
buffer substance and if appropriate after concentrating or diluting, can be used
directly as liquid preparation for dyeing.
The present invention thus also relates to the use of the dyes of the invention for
dyeing or printing these materials and to processes for dyeing or printing these
materials in a conventional manner, by using dyes of the invention as a colorant. The
materials are preferably employed in the form of fiber materials, especially in the
form of textile fibers, such as woven fabrics or yarns, as in the form of hanks or
wound packages.
Hydroxyl-containing materials are those of natural or synthetic origin, for example
cellulose fiber materials or their regenerated products and polyvinyl alcohols.
Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such
as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example
staple viscose and filament viscose.
Carboxamido-containing materials are for example synthetic and natural polyamides
and polyurethanes, especially in the form of fibers, for example wool and other
animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.
The dyes of the invention can be applied to and fixed on the substrates mentioned,
especially the fiber materials mentioned, by the application techniques known for
water-soluble dyes, especially fiber-reactive dyes.
For instance, on cellulose fibers they produce by the exhaust method from a long
liquor using various acid-binding agents and optionally neutral salts, such as sodium
chloride or sodium sulfate, dyeings having very good washfastnesses. Application is
preferably from an aqueous bath at temperatures between 40 and 105°C, optionally
at a temperature of up to 130°C under superatmospheric pressure, and optionally in
the presence of customary dyeing auxiliaries. One possible procedure is to introduce
the material into the warm bath and to gradually heat the bath to the desired dyeing
temperature and to complete the dyeing process at that temperature. The neutral
salts which accelerate the exhaustion of the dyes may also, if desired, only be added
to the bath after the actual dyeing temperature has been reached.
The padding process likewise provides excellent color yields and very good color
build-up on cellulose fibers, the dyes being allowed to become fixed on the material
by batching at room temperature or at elevated temperature, for example at up to
60°C, by steaming or using dry heat in a conventional manner.
Similarly, the customary printing processes for cellulose fibers, which can be carried
out either single-phase, for example by printing with a print paste comprising sodium
bicarbonate or some other acid-binding agent and by subsequent steaming at 100 to
103°C, or two-phase, for example by printing with a neutral or weakly acidic print
color and subsequent fixation either by passing the printed material through a hot
electrolyte-comprising alkaline bath or by overpadding with an alkaline electrolyte-
comprising padding liquor with subsequent batching of the alkali-overpadded
material or subsequent steaming or subsequent treatment with dry heat, produce
strong prints with well-defined contours and a clear white ground. The appearance of
the prints is not greatly affected by variations in the fixing conditions.
When fixing by means of dry heat in accordance with the customary thermofix
processes, hot air from 120 to 200°C is used. In addition to the customary steam at
101 to 103°C, it is also possible to use superheated steam and high-pressure steam
at temperatures of up to 160°C.
The acid-binding agents which effect the fixation of the dyes of the invention on the
cellulose fibers include for example water-soluble basic salts of the alkali metals and
likewise alkaline earth metals of inorganic or organic acids or compounds which
liberate alkali in the heat. Especially suitable are the alkali metal hydroxides and
alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali
metal compounds being the sodium and potassium compounds. Such acid-binding
agents include for example sodium hydroxide, potassium hydroxide, sodium
carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium
dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate,
waterglass or trisodium phosphate.
The cellulose dyeings obtained following the customary aftertreatment by rinsing to
remove unfixed dye portions exhibit very good dye properties and provide by the
application and fixing methods customary in the art for fiber-reactive dyes strong
dark blue dyeings and prints having very good fastness properties, especially very
good wash-, light-, alkali-, acid-, water-, seawater-, perspiration- and rubfastnesses,
on the materials mentioned in the description, such as cellulose fiber materials,
especially cotton and viscose. The dyeings are further notable for their high degree
of fixation and good build-up on cellulose materials. Of particular advantage is the
good washfastness of the dyeings, the high fixation value and the low temperature
dependence compared with the prior art.
Furthermore, the dyes 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 finish (cf. for
example H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd Edition (1972), p.
295-299, especially the finish by the Hercosett process (p. 298); J. Soc. Dyers and
Colourists 1972, 93-99, and 1975, 33-44) can be dyed with very good fastness
properties.
The process of dyeing on wool is here carried out in a conventional manner from an
acidic medium. For instance, acetic acid and/or ammonium sulfate or acetic acid and
ammonium acetate or sodium acetate may be added to the dyebath to obtain the
desired pH. To obtain a dyeing of acceptable levelness, it is advisable to add a
customary leveling agent, for example on the basis of a reaction product of cyanuric
chloride with 3 times the molar amount of an aminobenzenesulfonic acid and/or of an
aminonaphthalenesulfonic acid or on the basis of a reaction product of for example
stearylamine with ethylene oxide. For instance, the dyes of the invention are
preferably subjected to the exhaust process initially from an acidic dyebath having a
pH of about 3.5 to 5.5 under pH control and the pH is then, toward the end of the
dyeing time, shifted into the neutral and optionally weakly alkaline range up to a pH
of 8.5 to bring about, especially for very deep dyeings, the full reactive bond between
the dyes 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
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
temperatures of up to 106°C. Since the water solubility of the dyes of the invention is
very good, they can also be used with advantage in customary continuous dyeing
processes. The dyes of the invention dye the materials mentioned in deep blue
shades.
The examples hereinbelow serve to illustrate the invention. Parts and percentages
are by weight, unless otherwise stated. The compounds described in the examples in
terms of a formula are partly indicated in the form of free acids; in general these
compounds are prepared and isolated in the form of their salts, preferably sodium or
potassium salts, and used for dyeing in the form of their salts. The starting
compounds mentioned in the following examples, especially table examples, can
similarly be used in the synthesis in the form of the free acid or in the form of their
salts, preferably alkali metal salts, such as sodium or potassium salts.
Example 1
377 parts of 4-b-sulfatoethylsulfonyl-2-aminophenol-6-sulfonic acid are diazotized
with sodium nitrite and coupled at pH 6-7 onto 239 parts of 2-amino-5-
hydroxynaphthalene-7-sulfonic acid. This monoazo compound
is diazotized and coupled onto 361 parts of N-acetamino-3,6-disulfo-8-
hydroxynaphthalene
The resultant bisazo dye
is subsequently metallized with 245 parts of copper sulfate pentahydrate. The blue
dye obtained, which conforms to the formula A
(A max. = 587nm)
is salted out with sodium chloride, filtered off and dried at 50°C under reduced
pressure. The dye produces strong dark blue dyeings and prints on cotton which
have very good fastnesses, among which the light-, wash-, water- and
perspirationfastnesses and also the fastness to chlorinated water, solvents, crocking
and hot pressing may be singled out in particular.
The table examples which follow describe further dyes of the general formula (1-A)
according to the invention. The dyes, when applied by the dyeing methods
customary for reactive dyes, provide deep blue dyeings having good all-round
fastnesses on cotton for example.
The process described in example 1 likewise provides the hereinbelow mentioned
compounds of the general formula (I-B). When applied by the dyeing methods
customary for reactive dyes, they provide yellowish to brownish red dyeings having
good all-round fastnesses on cotton for example.
The process described in example 1 likewise provides the hereinbelow mentioned
compounds of the general formula (I-C). When applied by the dyeing methods
customary for reactive dyes, they provide yellowish to brownish red dyeings having
good all-round fastnesses on cotton for example.
WE CLAIM:

1. Water soluble fiber reactive disazo dyes of formula (1)
where
M is hydrogen or ammonium,
v is 0 or 1 and
Z is -CH=CH2 or -CH2CH2Z1,
where
Z1 is hydroxyl, chlorine, thiosulfato or sulfato, and
R1 is hydrogen or C1-C4-alkyl;
R2 is a moiety of the general formulae (2), (3), (4) or (5)
where
T1 is hydrogen, methyl, fluorine or chlorine,
T2 is hydrogen, fluorine or chlorine with the proviso that T2 and T1 are not both
hydrogen;
T3 is hydrogen, fluorine or chlorine;
A is C1 to C4-alkyl which may be substituted by up to two substituents selected
from the group consisting of chloro, bromo, hydroxyl and carboxyl, C2 to C4
alkenyl which may be substituted by up to two substituents from the group
consisting of chloro, bromo and hydroxyl, or phenyl,
L is phenylene or C2 to C6 alkylene;
Z is-CH=CH2,-CH2CH2Z1,
where
Z1 is hydroxyl, chlorine, thiosulfato or sulfato.
2. Water soluble fiber reactive disazo dyes as claimed in claim 1 wherein R2 is a
moiety of the general formula (4).
3. Water soluble fiber reactive disazo dyes as claimed in claim 1 or 2 wherein v is 0.
4. Water soluble fiber reactive disazo dyes as claimed in one of claims 1 to 3
wherein in formula (1) the SO2Z group is meta to the azo group.
5. Water soluble fiber reactive disazo dyes as claimed in one of claims 1 to 4,
wherein R2 is a CH3CO- radical.
6. The process for preparing water soluble fiber reactive disazo dyes as claimed in
claim 1 by diazotization of a compound of formula (6)
and coupling onto the compound of formula (7)
and subsequent diazotization of the resulting compound of formula (8)
and coupling at a pH of 6 to 9, onto the compound of formula (9)
followed by a coppering reaction with copper sulfate pentahydrate.
7. A process for dyeing or printing hydroxyl- and/or carboxamido-containing material
by applying one or more water soluble fiber reactive disazo dyes in dissolved form to
the material and fixing the dye or dyes on the material by means of heat or with the
aid of an alkaline agent, which comprises using dyes as claimed in one of claims 1 to
5.
8. A dye preparation comprising a dye as claimed in one of claims 1 to 6.
The invention relates to dyes of general formula (1) in which R11, R2, M, Z, v and
x are defined as cited in claim 1 to the production of the same and to the use of
said dyes for colouring or printing material containing hydroxy and/or
carbonamide groups, preferably fibrous material.

Documents:

01855-kolnp-2004-abstract.pdf

01855-kolnp-2004-claims.pdf

01855-kolnp-2004-correspondence.pdf

01855-kolnp-2004-description (complete).pdf

01855-kolnp-2004-form 1.pdf

01855-kolnp-2004-form 18.pdf

01855-kolnp-2004-form 2.pdf

01855-kolnp-2004-form 3.pdf

01855-kolnp-2004-form 5.pdf

01855-kolnp-2004-gpa.pdf

01855-kolnp-2004-letter patent.pdf

01855-kolnp-2004-reply first examination report.pdf

01855-kolnp-2004-translated copy of priority document.pdf


Patent Number 216863
Indian Patent Application Number 01855/KOLNP/2004
PG Journal Number 12/2008
Publication Date 21-Mar-2008
Grant Date 19-Mar-2008
Date of Filing 06-Dec-2004
Name of Patentee DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG.
Applicant Address INDUSTRIEPARK HOCHST , GEBAUDE B-598 65926 FRANKFURT, GERMANY.
Inventors:
# Inventor's Name Inventor's Address
1 RUSS, WERNER BAD-WEIBACH-STRABE 65439 FLORSHEIM-WICKER, GERMANY
2 SCHWAIGER GUNTHER JOHANNESALEE 41 65929 FRANKFUR4T GERMANY
3 MEIER, STEFAN GEISENHEIMER STRASSE 88 60529 FRANKFURT , GERMANY
PCT International Classification Number C09B62/44
PCT International Application Number PCT/EP03/06027
PCT International Filing date 2003-06-10
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 102 25 859.7 2002-06-11 Germany