DISPERSE DYES
FIELD OF THE INVENTION
The present invention relates to novel disperse dyes and use thereof.
BACKGROUND OF THE INVENTION AND PRIOR ART
Traditionally, disperse dyes are used for dyeing synthetic fibers and its blend with other
fibers such as cellulose, polyurethane, nylon and wool by usual exhaust dyeing, continuous
dyeing and printing techniques.
Indian Patent application 2162/KOLNP/2009 which is the Indian Equivalent of
WO2008074719 and entitled "Disperse dye mixtures" discloses mixtures of disperse azo
dyes with anthraquinone or benzodifuranone dyes for the colouration of synthetic textile
materials. The said patent emphasizes on the disperse dyes mixtures to achieve desired
fastness properties.
Indian Patent number: IN 190551 (1700/DEL/94) which is the Indian equivalent of
WO950200014 relates to monoazo dyes and a process for colouring synthetic textile
materials, to synthetic textiles when coloured, to a process for the mass coloration of plastics,
to plastics when coloured, to certain novel azo dyes and to compositions containing azo dyes.
GN 197577 (935/DEL/2002) and GN 196765 (936/DEL/2002), divisional to Patent no: IN
19055 1 also teach process for the preparation of an azo dye compound.
Recently with changing trends, fashion and market requirement consumption of blended
fabrics is significantly increased. These new fabrics are made out of micro size fiber using
fine denier polyester fiber or blending fiber with polyurethane, nylon and wool. The fastness
properties of these new colored fabrics become worse with respect to light fastness and
sublimation fastness, particularly washing fastness when dyed or printed with conventional
disperse dyes.
To overcome limitations of light fastness and washing fastness in disperse dyes for synthetic
textiles, the inventors of the present invention we have developed range of disperse dyes with
excellent overall fastness properties particularly washing fastness.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide disperse azo dyes.
It is a further object of the present invention to provide disperse azo dyes that have excellent
washing fastness on the polyester fiber.
It is another object of the present invention to provide a process for colouration of synthetic
textile materials.
SUMMARY OF THE INVENTION
According to one aspect of the present invention there is provided Disperse Dyes of
following formula,
wherein,
X, Y and Z are, independently, hydrogen, halogen, cyano, nitro or S0 2F;
Wherein at least one of X, and Z is S0 2F.
R1 is hydrogen, methyl, hydroxyl or NHR4;
R2 is hydrogen, chloro or methoxy;
R3 is hydrogen, (C]-C4)-alkyl or -CH 2 (CH2)nCOOCH2CN;
R5 is hydrogen, (C1-C4)-alkyl or -CH 2 (CH2)mCOOCH2CN;
R4 is -COCH 3,-CO C2H5, -S0 2CH3 or S0 2C2H5;
n and m are independently 0,1 or 2.
with the proviso:
- When, Y and Z both are CI, R is other than methyl.
- When, R2 is Hydrogen and R3, R5 both are alkyl, R1 is selected from NHS0 2CH3
orNHS0 2C2H5.
Disperse dyes defined in the Formula (1) have excellent washing fastness and light fastness
o the polyester fiber.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
Disperse Azo Dyes are generally prepared by diazotization of primary aromatic amine and
subsequently coupled with suitable coupling component.
The present invention relates to disperse dyes and methods for applying these dyes to fibers.
The disperse dyes are used for dyeing polyester and its blends with other fibers such as
cellulose, polyurethane, nylon and wool by usual exhaust dyeing, continuous dyeing and
printing techniques. Recently the fastness properties of colored fibers become worse in light
fastness and sublimation fastness, particularly washing fastness, due to use of finer size
denier polyester fiber or blending fiber with polyurethane, nylon and wool. The excellent
dyestuff to endure this use is desired in this dyeing and printing field.
To solve these problems, the inventors of the present invention have engineered novel
disperse azo dyestuffs with excellent fastness properties, which are showed as formula (I).
IN2010/000851
4
X, Y and Z are, independently, hydrogen, halogen, cyano, nitro or S0 2F;
Wherein at least one of X, Y and Z is S0 2F.
R1 is hydrogen, methyl, hydroxyl or NHR4;
R2 is hydrogen, chloro or methoxy;
R3 is hydrogen, (C,-C )-aIkyl or-CH 2 (CH2) „COOCH2CN;
R5 is hydrogen, (C,-C )-alkyI or -CH 2 (CH2) COOCH2CN;
R4 is -COCH 3,-CO C2H5, -S0 2CH3 or S0 2C H5.
n and m are independently 0,1 or 2;
with the proviso:
- When, Y and Z both are CI, R is other than methyl.
- When, R2 is Hydrogen and R3, R5 both are alkyl, R1 is selected from NHS0 2CH3
or NHS0 2C H5.
Under appropriate conditions, primary aromatic amine can be successfully diazotized and
coupled with specially developed coupling component to get novel disperse dyes of formula
(1). These new disperse dyes possesses excellent washing and light fastness properties.
A particular aspect of the present invention provides a composition comprising a disperse
dye of the present invention and additionally at least on further ingredient conventionally
used in colouring application such as a disperse agent and optionally a surfactant or wetting
agent. The dye composition typically comprises from 10% to 65%, preferably 20% to 50%
by weight of the total dye as single component or mixture in solid medium.
The preferred dispersing agents are lignosulphonates, naphthalene sulfonic
acid/formaldehyde condensates and phenol/cresol/sulphanilic acid/formaldehyde condensates.
The preferred examples of wetting agent are alkyl aryl ethoxylates which may be
sulphonated or phosphate and typical examples of other ingredients which may be present are
inorganic salts, de-foamer such as mineral oil or nonanol, organic liquids and buffers.
Disperse agents may be present at from 80% to 400% on the weight of the dye mixtures.
Wetting agents may be used at from 0. 1% to 20% on the weight of the dye mixtures.
The disperse dye or mixtures of disperse dyes of the present invention is milled with suitable
dispersing agent using glass beads or sand in an aqueous medium. The compositions may
have further additions of dispersing agents, fillers and other surfactants and may be dried, by
a technique such as spray drying, to give a solid composition comprising from 1 % to 65%
by weight of dyestuff.
In case of dyeing with fiber materials, the dyestuffs are milled in water with dispersing agent
in usual method and the finished dyes are used for dyeing or printing in the liquid form or the
powder form after spray drying of the liquid. The each finished dye is used for dyeing and
printing in single or mixtures of two or the more of the present invention dyes.
In case of exhaust dyeing, the polyester fiber, the conjugated fiber and the blend fiber is dyed
in excellent fastness by high temperature dyeing, carrier dyeing and continuous dyeing. The
dyestuff of formula (1) may be used individually or as a mixture of derivatives of formula (1)
for dyeing and printing.
In the case of printing, the polyester fiber, the textile materials are processed in excellent
fastness by direct printing or discharge printing.
P T/IN2010/000851
6
Embodiment of the present invention will be described in more detail with reference to the
following examples, in which parts are by weight unless otherwise stated.
Examples:
The present invention is concretely explained as follows, but the present invention is not
limited in these examples.
Example-1:
Structural formula 2)
Example 1 of structural formula (2) is synthesized by following method:
40% nitrosyl sulfuric acid 3 ml is added to the mixture of 2:5-dichlorofluorosulfonyl aniline
2.0 g, acetic acid and propionic acid (86:14, 25ml) at 0-5 °C and stirred for 2 hrs below 5°C.
Coupler, N-ethyl-N-cyanomethoxy carbonylethylaniline (Cyano methyl 3-
(ethyl(phenyl)amino)propanoate) 2.1 g is dissolved in methanol 100 ml and the synthesized
diazotized solution is added into this coupler solution at 0-5 °C. The reaction mass is stirred
for Ihr below 5°C and filtered the crystal solid and washed with water.
The 7.0g of 50% wet cake is obtained. The yield is 80%. The max in acetone of example 1
dyestuff is 515 nm.
And then 2.0g of the obtained wet press cake is milled with 2.0g of naphthalenesulfonic acidformaldehyde
condensate and 50g of water and 500 g of glass beads (average side is 0.8mm
of diameter.) for 24 hr and after milling, the mass is filtered to separate glass beads.
The 20g of the obtained finished liquid is added in the 100 ml of water and kept the pH 4
with acetic acid, and lOg piece of polyester is added into the dye bath for exhaust dyeing.
The dyeing bath is heated to 135 °C and kept for 40min. After proper rinsing, washing and
drying, the dyed material gives deep Rubine shade with excellent washing fastness, light
fastness and sublimation fastness.
Fastness properties of the dyed fabrics are evaluated by following test method.
Washing Fastness as per Test Method AATCC 6 1 2A, Light Fastness as per Test Method
ISO 105 B02 and Sublimation Test at 80 deg for 30 sec and at 2 0 deg for 30 sec.
Example-2:
The dyestuffs of the formula (3) are synthesized using same methods described in Example- 1
to get following dyes described in table:
These dyestuffs show the excellent washing fastness, light fastness and sublimation fastness.
Example-3:
The dyestuffs of the formula (4) are synthesized using same methods described in Example-1
to get following dyes described in table:
These dyestuffs give very brilliant shades and show the excellent washing fastness, light
fastness and sublimation fastness.
Exampte-4:
The dyestuffs of the formula (5) are synthesized using same methods described in Example- 1
to get following dyes described in table:
These dyestuffs show the excellent washing fastness, light fastness and sublimation fastness.
Example-5:
The dyestuffs of the formula (6) are synthesized using same methods described in Example- i
to get following dyes described in table:
(6)
CH2(CH2)mCOOCH2CN
Example X Z R R R3 R4 m h, h
5-1 N0 2 H H H C2H5
— 1 523
5-2 S0 2F H H H C2H5
— 1 5 11
5-3 N0 2 H NHR4 H CH2COOCH2CN COCH3 0 546
5-4 N0 2 CI NHR4 H C2H5 S0 2CH3 1 570
5-5 N0 2 CI NHR4 OCH C2H5 COCH3 1 602
These dyestuffs show the excellent washing fastness, light fastness and sublimation fastness.
ExampIe-6:
The dyestuffs of the formula (7) are synthesized using same methods described in Example- 1
to get following dyes described in table:
These dyestuffs show the excellent washing fastness, light fastness and sublimation fastness.
/
Comparative Example 1
The following dyes written as dye of Example-37 in the Table- 1 of WO95/20014 is
compared with dyes written as dye Example-1 in this patent in Light Fastness, Washing
Fastness and Sublimation Fastness as follows.
WashingFastness as per Test Method AATCC 61 2A, Light Fastness as per Test Method ISO
105 B02 and Sublimation Test at 180 degfor 30 sec and at 210 degfor 30 sec.
Dye of Example-1 of this patent and Dye-37 of WO95/20014 are very similar chemicals only
except difference between ethyl group and C2H4COOCH2CN in amino radical. But the
quality differences are very big especially in washing fastness, also in sublimation fastness
and light fastness. This comparative example provides confirmation to the logical approach
to introduce two C2H4COOCH2CN substituents to improve washing fastness properties
instead of only one as in the case of WO95/20014. Introduction of two C2H4COOCH2CN
substituents gives more excellent washing fastness and also results in the improvement in
sublimation fastness and light fastness.
Comparative Example 2
In yet another approach to increase light fastness properties of Comparative Dye Example-37
of WO95/20014 inventors of this patent have introduced -NHS0 2CH3 or -NHS0 2C H5
substituent in the 3-(meta) position of coupling component and following comparison data
clearly shows superior properties achieved by intended changes:
WashingFastness as per Test MethodAATCC 61 2A, Light Fastness as per Test Method ISO
105 B02 and Sublimation Test at 180 degfor 30 sec and at 210 degfor 30 sec.
Dye of Example-3.2 of this patent and Dye-37 of WO95/20014 are very similar chemicals
only except difference between -NHS0 2C¾ in coupling component. But the quality
differences are very big especially in light fastness, also in sublimation fastness and washing
fastness. This comparative example provides confirmation to the logical approach to
introduce -NHS0 2CH3 substituent to improve Light Fastness properties of comparative Dye37
of the WO95/20014. Introduction of -NHS0 2CH3 substituent gives excellent light
fastness and also results in the improvement in sublimation fastness and washing fastness.
While the invention has been described in conjunction with specific embodiments thereof, it
is evident that many alternatives, modifications and variations will be apparent to those
skilled in the art in the light of forgoing description. Accordingly, it is intended to include all
such alternatives, modifications, and variations as set forth within the spirit and broad scope
of the appended claims.
CLAIMS
1.
wherein
X, Y and Z are, independently, hydrogen, halogen, cyano, nitro or S0 2F;
Wherein at least one of X, Y and Z is S0 2F.
R1 is hydrogen, methyl, hydroxyl or NHR4;
R2 is hydrogen, chloro or methoxy;
R3 is hydrogen, (C,-C4)-alkyl or -CH 2 (CH2) COOCH2CN;
R5 is hydrogen, (C C4)-alkyl or-CH 2 (CH2)mCOOCH2CN
R4 is ~COCH3,-CO C2H5, -S0 2CH3 or S0 2C2H5;
n and m are independently 0, 1or 2.
with the proviso:
When, Y and Z both are CI, R1 is other than methyl.
When, R2 is Hydrogen and R3, R4 both are alkyl, R1 is selected from NHS0 2CH3
orNHS0 2C2H5.
2. Novel disperse azo dyes according to claim 1 in which the compound of formula
3. Novel disperse azo dyes according to claim 1 in which the compound of formula
(1) is of formula (3):
Wherein
4. Novel disperse azo dyes according to claim 1 in which the compound of formula
(1) is of formula (4):
Wherein,
Novel disperse azo dyes according to claim 1 in which the compound of formula
(1) is of formula (5):
Wherein,
6. Novel disperse azo dyes according to claim 1 in which the compound of formula
(1) is of formula (6):
Where in,
7. Novel disperse azo dyes according to claim 1 in which the compound of formula
(1) is of formula (7):
Wherein
CI CI OH H C2H5 1
N0 2 H H H CH2COOCH2CN 1
CI CI NHR4 H C2H4COOCH2CN COCH 1
CI H CH3 H C H5 —" 1
8. A disperse dye composition according to any one of the preceding claims
comprising azo dye of formula (1) or a mixture thereof, dispersing agent in the
range of 80% to 400% by weight of the dye mixture and optionally a wetting
agent in the range for 0.1% to 20% by weight of the dye mixture.
9. Dyed material according to any one of the preceding claims as a single
component or in combination of two or more dyestuffs.