Note: Descriptions are shown in the official language in which they were submitted.
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This invention relates to the dyeing of textile
fabrics, and in particular to a continuous process for
dyeing textile fabrics formed at least partial]y of
polyester fibers.
It is known frotn the technical literature (for
example, W. Bernard Praxis des Bleichens und Faerbens von
Textilien [~leaching and Dyeing Practice of Textiles~,
Springer Verlag, 1966) and from pertinent publications that
textile fabrics of polyester fibers and/or their blends
with cellulosic fibers can be continuously dyed by the so-
called "Thermosol Process." In applying this method, the
fabric is impregnated with a cold to warm, aqueous disper-
sion of suitable dyestuffs and auxiliary agents to a
defined weight increase, dried, subsequently "thermally
fixed" at temperatures of 180 to 220C, and again liberated
from excessive dyestuff by washing. During the thermal
fixation, the dyestuffs diffuse into the polyester fi~er in
a finely dispersed or monomolecular form, and are dissolved
in the fiber. The advantage of this method is the possibi-
lity of simultaneously fixing the polyester fibers andobtaining very fast colors within a short period of time
ranging from 40 to 120 seconds at 180 to 220C~
A prerequisite for the success of the process is
that tl-e dyestuffs are already uniformly distributed in the
textile product after the impregnation and intermediate
drying. If not, nonuniform coloration will result.
Another prerequisite is that the product is dried before
the thermal fixation, since otherwise the temperatures for
the Thermosol Process will not be reached because of eva-
poration of the dyebaths.
However, the Thermosol method has been found
disadvantageous in practice, in that not all textile
fabrics of polyester fibers can be dyed by this process,
and that it is absolutely necessary to dry the product
following the padding. In particular, it is not possible
to dye pile fabrics by this method, since the dyebath
migrates to the pile tips and bases during the intermediate
drying, and thus, the product is dyed unevenly. Furthermore,
the process is uneconomical, since the fabric needs to be
dried twice during the dyeing process. Even though
attempts have been made to overcome these disadvantages by
the use of so-called migration inhibitors and special
padding assistants, they have been unsuccessful in the case
of the pile fabrics, such as, plushes, velvets and velours.
A further problem with the pile fabrics, due to their high
bulk and insulating characteristics, is that it is not
possible to achieve Thermosol temperatures throughout the
fabric in a reasonably short duration without overheating
and fusing the tips of the pile yarns or leaving inner por-
tions of the fabric insufficiently heated.
It is, therefore, an object of the present inven-
tion to develop a method for continuously dyeing polyester
fibers and filaments and/or their blends with cellulosic
fibers, which overcomes the aforementioned disadvantages
and by which also pile fabrics can be satisFactorily dyed.
Surprisingly, it has now been found that it is
possible to continuously dye textile fabrics of poLyester
fibers and filaments and/or their blends without having the
aforementioned disadvantages, when the fabrics are
809
impregnated in an aqueous dyebath, containing
(a) 0 to 5.0 g/l of a thickener;
(b) commercially available disperse dyestuffs in
an amount sufficient to dye the fibers to the
desired depth of color;
(c) 2 to 100 g/l of a partially sulfated
adduct of ethylene oxide with an alkyl phenol
or C8 to C16 fatty alcohol, preferably
nonylphenol or C12 fatty alcohol with ~ to 6
mols ethylene oxide;
(d) o to 60 g/l of nonionic or anionic sur-
factants; and
(e) 5 to 50 g/l of at least one organic com-
pound selected from the group consisting of
aromatic nitrile ethers and ethoxylated
chlorophenols.
The fabric is impregnated by any suitable method, such as
by padding, up to a weight increase of 60 to 25070, pre-
ferably, 80 to 160%, and is subsequently heated to a tem-
perature and for a time sufficient to fix the dyestuffs.
For example, the fabric may be steamed in the wet condition
for 1 to 20 minutes in a saturated vapor atmosphere of
96-105C, preferably 98-102C, then continuously washed at
20 to 60C in one to six baths, mechanically drained to a
residual moisture of 50 to 90%, and finally dried or 1 to
10 minutes, preferably 2 to 6 minutes, at temperatures of
140-210C, preferably, 170 to 200C.
The method of the present invention is charac-
erized in that it ls applicable to all fabric construc-
tion, and that intermediate drying is not needed. Based
on the special composition of the dyebath, it has thus been
made possible to dye polyester fibers, which could not be
dyed by steaming in a continuous process under the afore-
said conditions. Such a method has been so far unknown,
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and is both a considerable technical and economical advance
over the prior art (Thermosol Process).
The method of the present invention is applicable
to both conventional polyester (polyethyleneglycol-
terephthalate) fibers and other polyesters which are knownto the person skilled in the art under the term "easy
dyeable" or "carrier-free dyeable" polyester fibers, as well
as flame-resistant modified polyester fibers. This has so
far been only possible for li~ht shades. "Carrier-free
dyeable" is here understood that no carriers, i.e., com-
ponents, which are used to accelerate diffusion, are added to
the dyebath. The "carrier-free dyeable polyester fibers"
are modified conventional polyester fibers, which are pro-
duced by condensing polyethyleneglycols.
This method is also particularly suitable for
dyeing woven blends of polyester and cellulosic fibers.
Cellulosic fibers include both natural fibers, such as, for
example, cotton or linen, and regenerated fibers, such as,
for example, rayon or viscose, as well as esterified cellu-
losic fibers, such as, for example, diacetate or triace-
tate.
This method permits dyeing of the aforesaid fibers
in their composition as textile fabrics, such as, for
examples, fleeces, tricots or knits, but, in particular,
woven fabrics. The textile fabrics may be both flat
fabrics and, particularly, pile fabrics, such as, for
example, velvet, plush or velours. The method is espe-
cially suited for dyeing polyester pile fabrics, which
heretofore could not be successfully dyed in a continuous
process.
Of essential importance for the invention is the
composition of the dyebath. The individual operations for
application of the dyebath, such as immersion, padding,
spraying, scraping on, application of foam, impregnation;
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and the subsequent treatments, such as steaming, washing,
and clrying are per se conventional steps and employ known
types of apparatus, as are described for example in ~.
Peter, "~rundlagen der Textilveredelung" [Basics of Textile
Finishing], 11th edition, ~eutscher Fachverlag, Frankfurt,
pp. 43-47 and pp. 233-237.
According to the invention, the textile fabrics
are impregnated in an aqueous dyebath by suitable appïication
methods, such as immersion, padding, spraying, scraping on, or
by the application of foam, up to a weight increase (wet pick-
up) of 60 to 250%, preferably 80 to 200%, and, in particular,
80 to 160%, then directly steamed in-their wet condition for 1
to 20 minutes, at 96-105C, preferably 98-102C, then again
washed several times at 20 to 60C, mechanically drained and
finally dried at 140 to 210C, preferably 170 to 200C, for 1
to 10 minutes, preferably 2 to 8 minutes, and in particular 2
to 6 minutes.
The impregnation bath is composed of:
(a) 0 to S g/l (preferably 0.5 to 3.0 g/l)
of a thickener;
(b) up to 150 g/l (preferably 0.05 to 150 g/l
and particularly 2 to 50 g/l)
commercially available disperse dyestuffs;
(b') up to 100 g/l (preferably 0.05 to 50 g/l, and
particularly 2 to 50 g/l)
commercially available direct dyestuffs;
(c) 2 to 100 g/l (preferably 5 to 60 g/l)
of a partially sulfated adduct of ethylene
oxide with an alkyl phenol or C8 to C16 fatty
alcohols, preferably nonylphenol or C12
fatty alcohol with 1 to 6 mols of ethylene
oxlde;
(d) 0 to 60 g/l (preferably 2 to 30 g/l) nonionic
or anioni.c surfactants, which mayl for example,
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comprise at least one member selected from the
group consisting of alkane sulfonates, alkylaryi
sulfonates, sulfonated carboxylic acid esters,
sulfonated carboxylic acid amides, or ~l~ to
C2s fatty acids; and preferably Cl2 to ~14
alkane mono-sulfonate or sodium
dioctylsulfosuccinate; and
(e) 5 to 50 g/l (preferably 5 to 20 g/l)
of at least one organic compourld selected
from the group consisting of aromatic
nitrile ethers or ethoxylated chlorophenols
in emulsified form.
The dyestuffs under (b ) may be used in addition to the
disperse dyestuffs of (b) when the fabric contains cellulosic
fibers or yarns in addition to the polyester fibers or yarns.
Suitable thickeners may include nonionic and/or
anionic products as can be derived from the addition of
ethylene oxide, from the oxidative or thermal decomposition
or, respectively, carboxymethylation of guar or locust bean
powder; or cellulose, starch or algin derivatives. Suitable
thickeners include carboxymethylcellulose, carboxymethyl-
starch, alginates, such as the sodiu~, potassium or ammonium
salts of algin. Particularly suitable are products derived
from the addition of ethylene oxide as well as products
with a 0.3 to 0.7 degree of substitution.
The method of the present invention may employ any of the
usual commercially available disperse dyestuffs generally
recognized as suitable for polyester. They may be used both
as dispersed powders and aqueous dispersions. Particularly
suitable are disperse dyestuffs with a relatively large mole-
cule and of a particularly high lightfastness. The disperse
dyestuffs ~ay be used both alone and in combination with
direct dyestuffs. From a chemical viewpoint, the disperse
dyestuffs belong to the class of the azo or anthraquinone
dyestuffs.
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I.ikewise, the usual commercially available
direct dyestuffs conventionally used for cellu'Losic fibers may
be employed in this process. They are water soluble and can
belong to the various chemical classes of dyestuf'fs, such as,
for example, azo dyestuffs, anthraquinone dyestuffs or
metallized dyestuffs. The dyestuffs particularly suita'ble for
the method of the present invention, are selected 'by their
solubility, high color absorption and high lightfastness.
Both the disperse and direct dyestuffs may contain the usual
dispersing and pulverizing assistants as well as diluent
substances or salts,
Also of importance for the present method is the use
of partially sulfated adducts of ethylene oxide with alkylphe-
nols or C8 to C16 fatty alcohols, identified above as com-
ponent (c). Preferred are partially sulfated adducts ofnonylphenol or C12 fatty alcohols with 1 to 6 mols ethylene
oxide. Specific examples include: the ammonium salt of a
partially sulfated adducts of nonylphenol with 5.5 mols ethy-
lene oxide, the sodium salt of a partially sulfated adduct of
nonylphenol with 4 mols ethylene oxide, the sodium salt of a
partially sulfated adduct of a C12 fatty alcohol with 2 mols
ethylene oxide, the ammonium salt of a partially sulfated
adduct of nonylphenol with 2.5 mols ethylene oxide, and the
ammonium salt of a partially sulfated adduct of octylphenol
with 6 mols ethylene oxide.
These products are obtained by the partial su'lfa-
tion of the adducts from ethylene oxide with alkyl phenols
or fatty alcohols respecti~7ely. The degree of the ethoxy-
lation and sulfation may widely vary, and the products are
obtained in the form of their ammonium or alkali, in par-
ticular sodium, salts. The component (c) acts as an
emulsifier and dispersant for the dyes and can be directly
added to the dyebath.
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The dyebath also desirably includes anionic and
nonionic surfactants, identified above as component (d).
Suitable surfactants may be selected from ammonium or
alkali metal salts of alkane sulfonates, sulfonated carboxyiic
acid esters, or sulfonated carboxylic acid amides. Pre-
ferred are C12 to C14 alkane monosulfona-tes or sodium
dioctylsulfosuccinate. Specific examples include: the
sodium salt of sulfosuccinic acid 2-ethylhexylester, the
sodium salt f C12 to C16 alkanesulfonate, and the sodium
salt of sulfosuccinic acid C12 hemi-amide.
These, in general, are wetting agents which are
known to the person skilled in the art under the descrip-
tion of rapid wetting agents. In the method of this inven-
tion, these agents serve as wetting agents during the
application stage and also serve to generate foam in the
steaming stage to promote level and even dyeing, especially
of pile fabrics. Chemically, they are C12 to C16 alkane
sulfonates, monoesters and diesters of sulfosuccinic acid, or
monoamides or diamides of sulfosuccinic acid. The component
(d) can be directly added to the dyebath. Also suitable are
ammonium or alkali metal salts of alkylarylsulfonates, such as
sodium dodecyl benzenesulfonate; ammonium or alkali metal
salts of lauryl sulfonate, such as sodium lauryl sulfonate;
ammonium or alkali metal salts of ethylene oxide adducts of
lauryl sulfonate, such as the sodium salt of the addition of 1
to 6 mols of ethylene oxide to lauryl sulfonate; and ammonium
or alkali metal salts of ethylene oxide adducts of C12 to C2s
fatty acids, an example of which is the adduct of 9 to 50
mols of ethylene oxide to octadecanoic acid~
Component (e) as described above may comprise
accelerators based on aromatic nitrile ethers or ethoxy-
lated chlorophenols in emulsified form, in particular, ben-
zyloxypropionitrile, chlorobenzyloxypropionitrile and
methylbenzyloxypropionitrile, as well as di-and triethylene
~ ~4~
glycol monochlorophenyl e-ther. Preferably the nitrile
e~ers have,a molecular weight of 100 to 250, in par~cular, 150
to 200, and that o~ the ethoxylated chlorophenols ranges fr~m 150
to 400, in particular from 200 to 300.
These products are water insoluble, high-boiling
liquids, which are capable of softening the polyester
fibers under the conditions of the method according to the
invention. Therefore, they make possible and accelerate
the diffusion of the dispexse dyes into the polyester
fibers.
Commercially available products of component (e)
are either pure substances or contain emulsifiers. Pure
substances are added with the aforesaid assistants to the
padding liquors in emulsified form. Particularly suita'ble
components (e) for the present method are di- and triethy-
leneglycol monochlorophenyl ethers and benzyloxypropio-
nitrile, Preferred emulsifiers for the component (e) are
ethoxylated ~16 to Clg fatty alcohols with 10 to 25 mols
ethylene oxide.
The described assistants (c), (d), and (e) can 'be
used both alone and combined with each other, and the sum
of the quantities used can vary from about 2 to about 200
g/l of the dyebath.
Aside from the aforesaid ingredients, the dyebath
may contain additional assistants, such as dispersing
agents, wetting agents, antistatic agents and defoamers.
The following examples are intended to describe
the invention in more detail, but not to limit it.
Example 1
A raschel plush product of polyester (Trevira 220)
was impregnated in a bath containing:
2.0 g/l modified guar powder (modified by tllermal
decomposition)
2.3 g/l Polyester Yellow LS (trade name)
0.5~ g/l Polyester Brilliant Red BS (trade name)
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0.3 g/l Polyester Violet 2RB (trade name)
1.23 g/l Polyester Blue 6102 (trade name)
25.0 g/l Ammonium salt of a partially sulfated adduct
of nonylphenol with 5,5 mols ethylene oxide;
10.0 g/l Sodium salt of the sulfosuccinic acid 2-ethyl-
hexyl ester;
15.0 g/l Benzyloxypropionitrile.
The material was impregnated on a padder with a 95~O
absorption of the bath. The product was then stearned for 10
minutes at 99C in a saturated vapor a-tmosphere, and sub-
sequently washed five times in 30C waterO
The material was then drained by squeezing to 75%
residual moisture, and finally dried for 3 minutes on a
tenter at 180C. A grey, very uniform pile fabric was
obtained with suitable lightfastness and good general ~ast-
nesses to rubbing (crocking) and washing.
Example 2
A pile fabric consisting of (55%) polyethylenegly-
coltherephthalate fibers in ~he pile and (45%) cotton in
the backing was preset for ~0 seconds at 190C. Then, the
fabric was impregnated by padding with a liquor consisting
of:
2,5 g/l locust bean powder ethoxylated with 1.S mols
ethylene oxide per OH group.
3.0 g/l Polyester Yellow LS (trade name)
12.0 g/l Polyester Yellow 7102 (trade name)
9.0 g/l Polyester Brilliant Red BS (trade name)
8.0 g/l Polyester Rubin ~L (trade name)
5.0 g/l Polyester Blue 6102 (trade name)
3.64 g/l Sirus Light Orange GGL (trade name)
4.55 g/l Direct Bordeaux BS (trade name)
3.18 g/l Solamin Blue VGRL 167% (trade name)
40.0 g/l Sodium salt of a partially sulfated adduct of
nonylphenol with 4 mols ethylene oxide
~2~ )9
18.0 g/l Sodium salt of sulfosuccinic acid 2-ethylhexyl
ester
30.0 g/l Benzyloxypropionitrile.
The absorption of the bath amounted to 98%.
The fabric was then steamed for 15 minutes at 98C
in a saturated vapor atmosphere, then washed three times in
50C water, mechanically drained to 75% residual moisture,
and dried for 2.5 minutes on a tenter at 190C. The result
was a dark red, uniformly dyed pile fabric with good fast-
nesses and a lightfastness of 7. The lightfastness was
determined in a]l examples according to both the Opel
Standards GME 60292 of 11/77 and by the FAKRA test.
Example 3
A woven velour of 55% polyester, 35% cotton and
10% rayon was impregnated by applying foam from a bath with
the following ingredients (80% absorption of the bath):
3.5 g/l water soluble guar derivative (l.O mol ethylene
oxide per OH group)
l,O g/l Polyester Yellow LS (trade name)
35 g/l Polyester Yellow 7102 (trade name)
1.3 g/l Polyester Brilliant Red BS (trade name)
1.05 g/l Polyester Blue BGL (trade name)
2.5 g/l Superlightfast Yellow EFC (trade name)
1.5 g/l Sirius Red F3B 200% (trade name)
1.25 g/l Sirius Light Grey CGLL 167% (trade name)
20.0 g/l Sodium salt of a partially sulfated adduct
of a Cl2 fatty alcohol with 2 mols ethylene oxide
5.0 g/l Sodium salt of a C12 to C16 alkane sulfonate
15.0 g/l 3-chlorophenol triethyleneglycol ether.
Following its impregnation, the material was
steamed for ~ minutes in a saturated vapor at 100C, washed
four times in 50C water, mechanically drained to 30~0 resi-
dual moisture and dried for 2 minutes at 200C. The result
was a light brown, completely uniformly dyed product with
excellent fastnesses.
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Example 4
A plush fabric with polyester pile and a cotton
and triacetate blend in the backing was impregnated in the
following bath:
1.5 g/l Anionically modified guar powder (degree of
carboxylation 0.53)
4.25 g/l Polyester Yellow 7102 (trade name)
4.02 g/l Polyester Brilliant Red BS (trade name)
10.1 g/l Polyester Blue 6102 (trade name)
1 0 2.6 g/l Solamin Blue VGRL 167% (trade name)
1.8 g/l Sirius Light Blue BRR 182% (trade name)
0.49 g/l Sirius Light Orange GGL (trade name)
0.77 g/l Sirius Light Brown R (trade name)
60.0 g/l NH4 salt of a partially sulfated adduct of
nonylphenol with 2.5 mols ethylene oxide
20.0 g/l Sodium salt of sulfosuccinic acid C12 hemi-amide
30.0 g/l emulslfier-containing methylbenzyloxypropionitrile.
Impregnation was done Gn a two-roller padder with
100~O absorption of the bath. Then the material was steamed
in its wet condition for 14 minutes in a 98C saturated
vapor atmosphere, subsequently continuously washed in 5
baths at 45C, and drained by squeezing to 65% resi-
dual moisture, and finally dried for 4 minutes on a
6-section tenter at 185C. The result was a medium to dark
blue, uniform coloration with a lightfastness of 7 and very
good general fastnesses.
Example 5
A liquor consisting of
4.5 g/l carboxylated guar derivative
(degree of carboxylation 0.40)
1.0 g/l Polyester Yellow LS (trade name)
3.5 g/l Polyester Yellow 7102 (trade name)
1.3 g/l Polyester Brilliant Red BS (trade name)
1.05 g/l Polyester Blue B(;L (trade name)
2.5 g/l Superlightfast Yellow EFC (trade name)
~2~ 36)9
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1.5 g/l Sirius Red F3B 200% (trade namej
1.25 g/l Sirius Light Grey CGLL 167% (trade name)
35.0 g/l NH4 salt of a partially sulfated adduct of
octylphenol with 6 mols ethylene oxide
10.0 g/l Chlorobenzyloxypropionitrile
was scraped with a 200% absorption of the bath on a tricot of
7070 carrier-free dyeable polyester, 20% cotton, and 10%
rayon, which was then steamed for 15 minutes at 98C. It was
then washed three times at 45C and drained to 80~ residual
moisture, and finally dried for 8 minutes at 160C. The
resul~ was a blue grey, uniform coloration with excellent
fastnesses. The lightfastness according to the so-called
"Opel Test" ranged from 6 to 7.
Example 6
A tricot product of 100 percent polyester was pre-
set for 45 seconds at 180 C. Then the fabric was
impregnated by padding wi~h a liquor consisting of:
2 g/l Locust bean powder
15 g/l Polyester Brilliant ~ed BS (trade name)
4 g/l Polyester ~ubin GL (trade name)
2.3 g/l Polyester Blue 6102 (trade name)
50 g/l Sodium salt of a partially sulfated adduct of
nonylphenol with 4 mols ethylene oxide
25 g/l Sodium salt of sulfosuccinic acid 2-ethylhexyl
ester
25 g/l Benzyloxypropionitrile
The absorption of the bath amounts to 86~o~ The fabric was
steamed for 9 minutes at 99 C in a saturated vapor
atmosphere and then washed three times in 50 C water,
mechanically drained to 80% residual moisture, and dried
for 2 minutes on a tenter at 180 C. The result was a dark
red, uniformly dyed fabric with good fastness.
