Disperse dye compositions

A dye composition containing at least one turquoise blue monoazo dye of the formula (I): ##STR1## and at least one additional dye which is at least one yellow monoazo dye of the formula (II): ##STR2## or at least one blue anthraquinone dye of the formula (III): ##STR3## or at least one navy blue dye of the formula (IV): ##STR4##

The present invention relates to disperse dye compositions. Particularly, 
it relates to green, turquoise blue and navy blue disperse dye 
compositions which are excellent in the temperature dependency in high 
temperature dyeing, the build up property and the sublimation fastness. 
In dyeing, it is common to blend various dyes to dye fabrics with a desired 
color. However, it is often difficult to obtain a desired color or to 
obtain a dye composition having good dyeing properties, since dyeing 
properties of the dyes to be blended are different. 
In recent years, in a research for developing disperse dyes capable of 
dyeing polyester fibers with turquoise blue, a study has been made to 
develop a disperse dye composition containing as the main component a 
monoazo dye having high tinctorial strength as compared with an 
anthraquinone-type turquoise blue dye, which is excellent in the pH 
dependency and the temperature dependency at the time of dyeing and which 
is excellent also in the build up property and the sublimation fastness. 
However, a disperse dye composition which is fully satisfactory has not 
yet been developed. 
The present inventors have conducted extensive studies to develop a dye 
composition capable of dyeing polyester fibers with blue color, and as a 
result, have found blue dye compositions, particularly turquoise blue, 
navy blue and green disperse dye compositions, which are excellent in the 
temperature dependency in dyeing, the build up property and the 
sublimation fastness and which have high tinctorial strength. The present 
invention has been accomplished on the basis of this discovery. 
The present invention provides a green dye composition comprising at least 
one turquoise blue monoazo dye of the following formula (I): 
##STR5## 
wherein each of R.sup.1 and R.sup.2 which are independent of each other, 
is a C.sub.1 -C.sub.5 alkyl group, an allyl group or a C.sub.1 -C.sub.4 
alkoxy C.sub.2 -C.sub.3 alkyl group, R.sup.3 is a C.sub.1 -C.sub.5 alkyl 
group, a C.sub.1 -C.sub.4 alkoxy C.sub.2 -C.sub.3 alkyl group or a phenyl 
group, R.sup.4 is a hydrogen atom, a halogen atom or a methyl group, and Z 
is an oxygen atom or a sulfur atom, and at least one yellow monoazo dye of 
the following formula (II): 
##STR6## 
wherein A is a hydrogen atom, a halogen atom, 
##STR7## 
(wherein W is a C.sub.4 -C.sub.8 alkyl group), 
##STR8## 
(wherein W is as defined above) or 
##STR9## 
B is a hydrogen atom or a nitro group, and R.sup.5 is a C.sub.1 -C.sub.8 
alkyl group or a C.sub.1 -C.sub.3 alkoxy C.sub.1 -C.sub.3 alkyl group. 
Further, the present invention provides a turquoise blue dye composition 
comprising at least one dye of the formula (I) and at least one blue 
anthraquinone dye of the following formula (III): 
##STR10## 
wherein R.sup.6 is a C.sub.3 -C.sub.4 alkyl group, a C.sub.1 -C.sub.4 
alkoxy C.sub.2 -C.sub.3 alkyl group or a C.sub.1 -C.sub.2 alkoxy C.sub.2 
-C.sub.3 alkoxy C.sub.2 -C.sub.3 alkyl group. 
Still further, the present invention provides a navy blue dye composition 
comprising at least one dye of the formula (I) and at least one navy blue 
dye of the following formula (IV): 
##STR11## 
wherein X is a halogen atom, Y is a hydrogen atom, a C.sub.1 -C.sub.2 
alkoxy group or a C.sub.1 -C.sub.2 alkoxy C.sub.1 -C.sub.2 alkoxy group, 
R.sup.7 is a C.sub.1 -C.sub.5 alkyl group, and each of R.sup.8 and R.sup.9 
which are independent of each other, is a hydrogen atom, an allyl group or 
a C.sub.1 -C.sub.5 alkyl group, provided that R.sup.8 and R.sup.9 are not 
simultaneously hydrogen atoms. 
In the accompanying drawing, FIG. 1 is the X-ray diffraction pattern of the 
turquoise blue dye used in Example 1 of the present invention, wherein the 
abscissa represents the diffraction angle (2.theta.), and the ordinate 
represents the diffraction intensity. 
Now, the present invention will be described in detail with reference to 
the preferred embodiments. 
In the above formulas (I) to (IV), the C.sub.1 -C.sub.5 alkyl group for 
each of R.sup.1, R.sup.2, R.sup.3, R.sup.7, R.sup.8 and R.sup.9 may, for 
example, be a straight chain or branched chain C.sub.1 -C.sub.5 alkyl 
group such as a methyl group, an ethyl group, a n-propyl group, an 
i-propyl group, a n-butyl group, a sec-butyl group or a n-pentyl group. 
The C.sub.1 -C.sub.4 alkoxy C.sub.2 -C.sub.3 alkyl group for each of 
R.sup.1, R.sup.2, R.sup.3 and R.sup.6 may, for example, be a methoxyethyl 
group, an ethoxyethyl group, a methoxypropyl group, an ethoxypropyl group, 
a propoxyethyl group, a propoxypropyl group, a butoxyethyl group or a 
butoxypropyl group. 
The halogen atom for each of R.sup.4, A and X may, for example, be a 
chlorine atom, a bromine atom or a fluorine atom. Particularly preferred 
is a chlorine atom or a bromine atom. 
The C.sub.1 -C.sub.8 alkyl group for R.sup.5 may, for example, be n-hexyl 
group, a n-octyl group or a 2-ethylhexyl group in addition to the 
above-mentioned C.sub.1 -C.sub.5 straight chain or branched chain alkyl 
group, and the C.sub.1 -C.sub.3 alkoxy C.sub.1 -C.sub.3 alkyl group for 
R.sup.5 may, for example, be a methoxypropyl group, an ethoxypropyl group 
or an i-propoxypropyl group. 
As the C.sub.1 -C.sub.4 alkoxy C.sub.2 -C.sub.3 alkyl group for R.sup.6, a 
methoxypropyl group, an ethoxypropyl group or a propoxypropyl group is 
preferred, and the C.sub.1 -C.sub.2 alkoxy C.sub.2 -C.sub.3 alkoxy C.sub.2 
-C.sub.3 alkyl group for R.sup.6 may, for example, be a 
methoxyethoxypropyl group, an ethoxyethoxypropyl group, a 
methoxypropoxyethyl group or an ethoxypropoxypropyl group, preferably a 
methoxyethoxypropyl group. 
W is preferably a 2-ethylhexyl group or a n-octyl group. 
Y is preferably a hydrogen atom, a methoxy group or a methoxyethoxy group. 
Among dyes of the formula (I), preferred is a dye wherein each of R.sup.1 
and R.sup.2 is a C.sub.2 -C.sub.3 straight chain alkyl group, R.sup.3 is a 
C.sub.1 -C.sub.2 alkyl group or a C.sub.1 -C.sub.4 alkoxy C.sub.2 -C.sub.3 
alkyl group, R.sup.4 is a hydrogen atom, and Z is an oxygen atom. 
Particularly preferred is a dye wherein each of R.sup.1 and R.sup.2 is an 
ethyl group, R.sup.3 is a methyl group, R.sup.4 is a hydrogen atom, and Z 
is an oxygen atom, which has a crystal structure characterized by X-ray 
diffraction peaks as defined hereinafter. 
FIG. 1 is an X-ray diffraction pattern of a dye obtained by applying 
specific treatment to a cake of a dye having the above-mentioned 
substituents, obtained by recording the diffraction state by CuK.alpha. 
rays in powder X-ray diffractometory by means of a proportional counter, 
wherein the abscissa represents the diffraction angle (2.theta.), and the 
ordinate represents the diffraction intensity. As shown in FIG. 1, 
relatively strong peaks are observed at diffraction angles (2.theta.) of 
9.4.degree., 25.6.degree. and 26.6.degree., and intermediate peaks are 
observed at diffraction angles (2.theta.) of 6.4.degree., 13.1.degree., 
22.2.degree. and 28.1.degree.. The above numerical values of the X-ray 
diffraction angles may shift to either plus or minus within a range of 
about .+-.0.2. 
As the specific treatment to obtain the dye having the above-mentioned 
crystalline structure, it is possible to employ, for example, 1 a method 
wherein the dye cake having the amorphous structure is dispersed in an 
aqueous medium and subjected to stirring treatment at a temperature of 
from 60.degree. to 130.degree. C., preferably from 80.degree. to 
100.degree. C., for from 0.5 to 30 hours, preferably from 1 to 10 hours, 
if necessary in the presence of a dispersant such as a condensate of 
naphthalenesulfonic acid with formaldehyde or a concentrate of a sulfite 
pulp waste liquor containing sodium lignin sulfonate as the main 
component, 2 a method wherein the dye cake having the amorphous structure 
is dispersed in an organic solvent, for example, an alcohol such as 
methanol, ethanol or butanol, an ether such as dioxane, ethylene glycol, 
or glycol ether and subjected to stirring treatment at a temperature of 
from 15.degree. to 100.degree. C., preferably from 20.degree. to 
80.degree. C., for from 0.5 to 10 hours, or 3 a method wherein 
2-amino-5-nitro-3-cyanothiophene is diazotized by a conventional method, 
followed by coupling with 3-methoxyacetylamino-N,N-diethylaniline as a 
coupler in an alcoholic medium, such as methanol or ethanol, or in an 
organic solvent such as ethylene glycol or glycol ether at a temperature 
of from 5.degree. to 30.degree. C., for from 1.0 to 10 hours. 
Among dyes of the formula (II), preferred is a dye wherein A is 
##STR12## 
and R.sup.5 is a C.sub.1 -C.sub.3 alkyl group. 
Among dyes of the formula (III), preferred is a dye wherein R.sup.6 is a 
C.sub.1 -C.sub.2 alkoxy C.sub.2 -C.sub.3 alkoxy group or a C.sub.1 alkoxy 
C.sub.2 alkoxy C.sub.2 -C.sub.3 alkyl group. 
Among dyes of the formula (IV), preferred is a dye in which X is a chlorine 
atom or a bromine atom, Y is a hydrogen atom, a methoxy group or a 
methoxyethoxy group, R.sup.7 is a methyl group or an ethyl group, R.sup.8 
is a hydrogen atom or a C.sub.2 -C.sub.3 alkyl group, and R.sup.9 is a 
C.sub.2 -C.sub.3 alkyl group. 
By blending the turquoise blue dye of the formula (I) and the yellow dye of 
the formula (II), it is possible to obtain a green dye composition which 
is excellent in the temperature dependency, the build up property and the 
sublimation fastness. In this case, the blend ratio is preferably such 
that the yellow dye of the formula (II) is in an amount of from 0.03 to 
1.5 times by weight, particularly preferably from 0.1 to 1.0 time by 
weight, relative to the turquoise blue dye of the formula (I). 
Further, when the turquoise blue dye of the formula (I) is blended with the 
blue anthraquinone dye of the formula (III), it is possible to obtain a 
blue dye composition which is excellent in the light fastness, the 
sublimation fastness, the brightness, the leveling property, the 
temperature dependency, the build up property and the pH dependency and 
which is well balanced in these dyeing properties. In this case, the blend 
ratio is preferably such that the blue anthraquinone dye of the formula 
(III) is from 0.5 to 5 times by weight, particularly preferably from 1 to 
4 times by weight, relative to the turquoise blue dye of the formula (I). 
Further, when the turquoise blue dye of the formula (I) is blended with the 
navy blue dye of the formula (IV), it is possible to obtain a navy blue 
dye composition which is excellent in the temperature dependency, the 
build up property and the sublimation fastness and which has a low color 
rendering property under various light sources. In this case, the blend 
ratio is preferably such that the navy blue dye of the formula (IV) is 
from 0.03 to 2.0 times by weight, particularly preferably from 0.1 to 1.2 
times by weight, relative to the turquoise blue dye of the formula (I). 
Fibers dyeable by the disperse dye compositions of the present invention 
may, for example, be polyester fibers made of polyethylene terephthalate, 
polybutylene terephthalate or a polycondensation product of terephthalic 
acid with 1,4-bis(hydroxymethyl)cyclohexane, or a mixed fiber product such 
as a blended yarn fabric or a combined yarn fabric comprising natural 
fibers such as cotton, silk or wool and the above-mentioned polyester 
fibers. 
The dye compositions of the present invention are insoluble or hardly 
soluble in water. Accordingly, they may be dispersed in an aqueous medium 
by using, as a dispersant, a condensation product of naphthalene sulfonic 
acid with formaldehyde, a higher alcohol sulfuric acid ester or a higher 
alkylbenzene sulfonate to obtain a dyeing bath or a printing paste. Fibers 
can be dyed by dip dyeing (exhaustion dyeing) or printing. 
For example, in the case of dip dyeing, polyester fibers or fiber mixture 
products thereof can be dyed with good color fastness by common dyeing 
methods, such as a high temperature dyeing method or a thermosol dyeing 
method. In such a case, it is sometimes possible to obtain better results 
by an addition of a known acidic substance such as formic acid, acetic 
acid, phosphoric acid or ammonium sulfate to the dyeing bath. Further, it 
is usually preferred to adjust the pH of the dyeing bath within a range of 
from 4.0 to 8.0. The dyeing temperature may, for example, be at a level of 
from 120.degree. to 140.degree. C. 
The disperse dye compositions of the present invention exhibit particularly 
excellent dyeing properties and temperature dependency when they are 
applied to dip dyeing. Dyeing conditions in the dip dyeing are not 
particularly limited. For example, the dyeing temperature may be at a 
level of from 120.degree. to 140.degree. C., and the dyeing time may be at 
a level of from 30 to 60 minutes. The pH of the dyeing bath may be at a 
level of from 4.0 to 8.0. 
Further, for the purpose of adjusting the shade of the dyed products, at 
most 0.1 time by weight of other yellow, red or blue disperse dyes may be 
combined to the disperse dye compositions of the present invention. 
Now, the present invention will be described in further detail with 
reference to Examples. However, it should be understood that the present 
invention is by no means restricted to such specific Examples.

EXAMPLE 1 
140 g of a lignin sulfonic acid-formalin condensation product and 650 g of 
water were mixed to 30 g of a turquoise blue dye of the following formula 
(I-1) as the dye of the formula (I) which had a crystal structure 
characterized by an X-ray diffraction pattern (CuK.alpha.) showing 
relatively strong peaks at diffraction angles (2.theta.) of 9.4.degree., 
25.6.degree. and 26.6.degree. and intermediate peaks at diffraction angles 
(2.theta.) of 6.4.degree., 13.1.degree., 22.2.degree. and 28.1.degree. and 
10 g of a yellow dye of the following formula (II-1) as the dye of the 
formula (II). The mixture was subjected to colloid milling by a sand 
grinder and then spray-dried. 
##STR13## 
To each of 0.1 g and 0.4 g of this powdery disperse dye composition, 0.08 g 
of a nonionic leveling agent (Diaserver.RTM. LR-PSL, manufactured by 
Mitsubishi Chemical Corporation) and 150 ml of water were added to obtain 
a dyeing bath. After adjusting the pH to 5.5, 5 g of a polyester cloth was 
immersed, and exhaustion dyeing was carried out at 130.degree. C. and 
120.degree. C. for 60 minutes, followed by soaping, washing with water and 
drying to obtain a dyed product of a green color having excellent leveling 
property. With respect to the dyed cloth, the temperature dependency, the 
build up property and the sublimation fastness were measured as will be 
described hereinafter, whereby the temperature dependency was 96, the 
build up property was 355, and the sublimation fastness was grade 4.sup.+. 
Temperature dependency: 
The dyed color density of the dyed cloth which was dyed at 130.degree. for 
60 minutes by using 0.1 g of the dye composition, was evaluated to be 100, 
and the dyed color density of the dyed cloth which was dyed at 120.degree. 
C. for 60 minutes under the same condition was represented by a relative 
value. The dyed color density was obtained as a K/S value from the 
reflectance of the dyed product measured by Macbeth 2020+. The ideal value 
is 100. 
Build up property: 
The dyed color density of the dyed cloth which was dyed at 130.degree. C. 
for 60 minutes by using 0.1 g of the dye composition, was evaluated to be 
100. Whereas, the dyed color density of the dyed cloth which was dyed 
under the same conditions by using 0.4 g of the dye composition was 
represented by a relative value. The dyed color density was measured in 
the same manner as for the temperature dependency. The ideal value is 400. 
Sublimation fastness: 
The dyed cloth which was dyed at 130.degree. C. for 60 minutes by using 0.1 
g of the dye composition, was treated at 180.degree. C. for 45 seconds in 
accordance with JIS L0879-1968, whereupon the staining degree of a nylon 
white cloth was evaluated by a gray scale. 
EXAMPLES 2-1 to 2-4 
Dyeing was carried out in the same manner as in Example 1 except that the 
yellow dye of the formula (II-1) used as the dye of (II) in Example 1 was 
changed to each of the following dyes of the formulas (II-2) to (II-5), to 
obtain dyed cloths of green color. The dyeing properties of the dyed 
cloths were evaluated in the same manner as in Example 1, whereby the 
temperature dependency was at least 90, the build up property was at least 
340, and the sublimation fastness was at least grade 4. 
##STR14## 
EXAMPLES 3-1 to 3-4 
Dyeing was carried out in the same manner as in Example 1 by using the dyes 
as identified in Table 1 in the amounts as identified in Table 1, as the 
dyes of the formulas (I) and (II), to obtain dyed cloths of green color. 
The dyeing properties of the dyed cloths were evaluated in the same manner 
as in Example 1, whereby the temperature dependency was at least 90, the 
build up property was at least 310, and the sublimation fastness was at 
last grade 4.sup.-. 
TABLE 1 
__________________________________________________________________________ 
Exam- 
ples 
(I) (II) 
__________________________________________________________________________ 
3-1 
##STR15## 20 g 
##STR16## 10 g 
3-2 
##STR17## 25 g 
##STR18## 5 g 
3-3 
##STR19## 9 g 
##STR20## 12 g 
##STR21## 9 g 
3-4 
##STR22## 22 g 
##STR23## 5 g 
__________________________________________________________________________ 
EXAMPLE 4 
140 g of a lignin sulfonic acid-formalin condensation product and 650 g of 
water were mixed to 10 g of a turquoise blue dye of the formula (I-1) as 
used in Example 1, as the dye of the formula (I) and 30 g of a blue 
anthraquinone dye of the following formula (III-1), as the dye of the 
formula (III). The mixture was subjected to colloid milling by a sand 
grinder and then spray-dried. 
Using 0.1 g and 0.4 g of this powdery dye composition, exhaustion dyeing 
was carried out at pH 5.5 at 130.degree. C. and 120.degree. C. for 60 
minutes in the same manner as in Example 1. The dyeing properties of the 
obtained dyed cloth were evaluated in the same manner as in Example 1, 
whereby the temperature dependency was 90, the build up property was 345 
and the sublimation fastness was grade 4.sup.+. 
##STR24## 
EXAMPLES 5-1 to 5-6 
Dyeing was carried out in the same manner as in Example 4 using the dyes as 
identified in Table 2 in the amounts as identified in Table 2, as the dyes 
of the formulas (I) and (III), whereby dyed cloths of turquoise blue 
having a temperature dependency of at least 85, a build up property of at 
least 310 and the sublimation fastness of at least grade 4, were obtained. 
TABLE 2 
__________________________________________________________________________ 
Exam- 
ples 
(I) (III) 
__________________________________________________________________________ 
5-1 
##STR25## 8 g 
##STR26## 32 g 
5-2 
##STR27## 20 g 
##STR28## 10 g 
##STR29## 10 g 
5-3 
##STR30## 15 g 
##STR31## 25 g 
5-4 
##STR32## 14 g 
##STR33## 13 g 
##STR34## 13 g 
5-5 
##STR35## 20 g 
##STR36## 20 g 
5-6 
##STR37## 15 g 
##STR38## 20 
__________________________________________________________________________ 
g 
EXAMPLE 6 
140 g of a lignin sulfonic acid-formalin condensation product and 650 g of 
water were mixed to 10 g of a turquoise blue dye of the formula (I-1) as 
used in Example 1, as the dye of the formula (I) and 10 g of a navy blue 
dye of the following formula (IV-1), as the dye of the formula (IV). The 
mixture was subjected to colloid milling by a sand grinder and then 
spray-dried. 
Using 0.1 g and 0.4 g of this powdery dye composition, exhaustion dyeing 
was carried out at pH 5.5 at 130.degree. C. and 120.degree. C. for 60 
minutes in the same manner as in Example 1, whereby dyed cloth of navy 
blue having a temperature dependency of 97, a build up property of 370 and 
a sublimation fastness of grade 4, was obtained. 
##STR39## 
Further, the color rendering property of the dyed cloth was evaluated in 
accordance with the following method, whereby the color was substantially 
the same even when the light source was different. 
Color rendering property: 
The color under standard A light of the dyed cloth which was dyed at 
130.degree. C. for 60 minutes at pH 5.5 by using 0.4 g of the dye 
composition was used as the standard, and the difference of the color 
under standard C light was visually evaluated. 
Further, when the dye of the formula (I-1) was not used, the dyed cloth was 
remarkably reddish under standard C light as compared with the color under 
standard A light. 
EXAMPLES 7-1 to 7-8 
Dyeing was carried out in the same manner as in Example 6 except that the 
turquoise blue dye of the formula (I) and the navy blue dye of the formula 
(IV) used in Example 6 were changed to those identified in Table 3, 
whereby dyed cloths of navy blue having a temperature dependency of at 
least 90, a build up property of at least 340 and a sublimation fastness 
of at least 4.sup.- and having a low color rendering property, were 
obtained. 
TABLE 3 
__________________________________________________________________________ 
Exam- 
ples 
(I) (IV) 
__________________________________________________________________________ 
7-1 
##STR40## 12 g 
##STR41## 5 g 
##STR42## 5 g 
7-2 
##STR43## 10 g 
##STR44## 12 g 
##STR45## 5 g 
7-3 
##STR46## 7 g 
##STR47## 5 g 
##STR48## 3 g 
7-4 
##STR49## 10 g 
##STR50## 5 g 
##STR51## 3 g 
7-5 
##STR52## 10 g 
##STR53## 5 g 
##STR54## 3 g 
7-6 
##STR55## 10 g 
##STR56## 5 g 
##STR57## 5 g 
7-7 
##STR58## 5 g 
##STR59## 10 g 
##STR60## 5 g 
7-8 
##STR61## 10 g 
##STR62## 5 g 
##STR63## 5 g 
__________________________________________________________________________ 
As described in the foregoing, the disperse dye compositions of the present 
invention are excellent in the temperature dependency, the build up 
property and the sublimation fastness, and they are capable of dyeing 
polyester fibers green, blue or navy blue. Thus, they contribute to 
enrichment of the dyeing techniques for polyester fibers.