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Патент USA US3066015

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United States Patent O?tice
3,006,005
Patented Nov. 27, 1962
1
3,066,005
PROCESS FOR THE TREATMENT OF HYDROXYL
GROUP-CONTAINING TEXTILE MATERIALS
Karlfried Wedemeyer, Koln-Stammheim, Karl Gustav
Kleb, Leverkusen, Heinz Adolf Dortmann, Bergisch
Gladbach, and Detlef Delis, Opladen, Germany, as
signors to Farbenfabriken Bayer Aktiengesellschaft,
Leverkusen, Germany, a corporation of Germany
, No Drawing. Filed Jan. 21, 1959, Ser. No. 788,049
Claims priority, application Germany Feb. 1, 1958
11 Claims. (Cl. 8-542)
10
The present invention relates to a process for the treat
ment of hydroxyl group-containing textile materials, par
ticularly of ?bres, fabrics and the like of native or re
generated cellulose, by applying to these materials in an 15
aqueous medium organic compounds having one or more
groups which can be alkylated together with polyfunc
tional compounds which contain as a functional group
ing —OSO3H or —-OSO3X groups, X being an alkali
metal cation, haloalkyl groups and/or epoxide groups, 20
capable of reacting with groups which can be alkylated,
on the one hand, and with the hydroxyl groups of the
materials to be treated, on the other hand, and by sub
jecting the material thus treated to the action of an ele
vated temperature in the presence of an acid-binding 25
agent. The process enables textile materials to be pro
duced particularly those which after treatment are fast to
wetting.
‘
The treatment of hydroxyl group-containing materials
may have various purposes such as the dyeing of ?bres 30
or fabrics, change of the feel of fabrics, hydrophobing,
application of optical bleaching agents, change of dye
ing capability with substantive dyestuifs, or other changes
of the properties of these materials. Depending on the
type of intended treatment, the components on which the
compounds with at least one group which can be alkyl
ated to be used according to the invention are based may
possess a widely varied composition.
They may be
dyestuffs, for example azo, azomethine, anthraquinone,
triphenylrnethane, oxazine or azoporphine dyestuffs. On 40
the other hand, ?uorescent compounds such as those of
the stilbene, benzimidazole, benzoxazole or benzthiozole
series may be used. In order to render textiles crease
resistant, the groups which can be alkylated may be
present in high molecular weight compounds.
CH3
As groups which can be alkylated and of which at
least one should be contained in the above mentioned
classes of compounds there are to be understood for ex~
ample: primary and secondary amino groups, sulphonic
acid amide groups, sulphonic acid alkylamide groups,
carboxylic acid amide and carboxylic acid alkylamide
groups, hydroxyl groups and mercapto groups.
The components on which the polyfunctional com
pounds of the aforesaid type are based may also have a
widely varied constitution. In addition to the aforesaid 55
basic compounds of the dyestuf‘f series, brightening agents,
hydrophobing agents and crease-proo?ng agents, these
alkyl
>—CHa—ll\T—OHr—OHz—OH—OHa—OH;-OH3
—SOsNa
compounds may also be colourless organic substances
Bifunctional groups as exempli?ed by those listed be
of any constitution, for example compounds of the ben 60 low are required only once in the molecule, but they may
also be present several times.
zene, diphenyl or naphthalene series. Polyfunctional
compounds as de?ned by the present invention are de
rivatives which are capable of reacting, by means of their
acid ester, haloalkyl or epoxide groups under the action
of an elevated temperature in the presence of an acid 65
binding agent, with the aforesaid organic compound
containing groups which can be alkylated as well as with
the hydroxyl groups of the material to be treated. Com
pounds of this type contain for example at least two
groupings of the same or different type as follows:
70
3,066,005
4
thus be impregnated, for example, with a solution of a
dyestu? containing a group which can be alkylated, dried
and then after-treated with an alkaline solution of a
polyfunctional compound of the above mentioned type
The polyfunctional compound acts to a. certain degree
as a bridge member between the hydroxyl group-contain
ing material and the groups which can be alkylated.
and, ?nally, ?xed at an elevated temperature. This proc
ess may also be carried out without intermediate drying,
if desired in the same bath.
Another modi?cation of the process consists in treat
The compounds with a group which can be alkylated
ing the fabric ?rst with a water-soluble polyfunctional
may also carry one or more mono- or polyfunctional 10 compound of the speci?ed type and then with a com
groups. The addition of compounds with polyfunctional
groups involves in this case an essentially higher yield in
?xation on the ?bre. Thus, a yellow dyestu? which
pound containing at least one group which can be alkyl
contains a group which can be alkylated and a reactive
ated, the action of the acid-binding agent being possible at
various stages of the process. Water-soluble polyfunc
tional compounds are inter alia those containing sulphuric
group capable of reacting with the ?bre, for example the
acid ester groups of the above mentioned type.
dyestuif
l-aminobenzene - 4 - sulphonic acid-?-hydroxy
alkyl - amide-sulphuric
acid
semiester~>1 - (3’ - amino
phenyl)-3-methyl-5-pyrazolone, may for example be ap
The treatment is expediently followed by a washing in
a neutral or Weakly alkaline aqueous bath. Amide group
containing materials such as wool, silk and the like may
plied to the ?bre together with a blue dyestu?C which con
be treated in the same manner in a weakly acid to neutral
tains at least two monofunctional or one polyfunctional 20 medium.
group, for example the reaction product from one mol
and ?xed to give a green dyeing of very good fastness to
If compounds with groups which can be alkylated or
polyfunctional compounds of the speci?ed type are used
which have dyestuft character, those dyestuffs are espe
cially advantageous for the dyeing process which possess
The application of mixtures of compounds containing
no or only a slight a?inity to the dyeing materials. The
use of these dyestu?’s enables a complete removal of the
of nickel-phthalocyanine-(S)-sic tetrasulphochloride and
4 mols of ,B-hydroxethylamino-sulphuric acid semiester,
wetting.
groups which can be alkylated, with polyfunctional com
ponents of the speci?ed type is preferably carried out in
an aqueous solution which may be treated with an acid—
binding agent such as alkaline substances, for example 30
alkali metal hydroxide or alkali metal carbonate, or
compounds convertible into alkaline substances such as
alkali metal bicarbonate. Further auxiliaries may be
added to the solution provided they do not react with
the starting compounds in an undesired manner. Such
dyestuff molecules not ?rmly ?xed to the ?bre in the
course of the dyeing process, to be completely removed
by a ?nal Washing in a neutral or alkaline aqueous bath.
It is known to apply dyestuffs having reactive groups,
for example those obtainable by condensation of amino
group-containing azo and anthraquinone dyestuffs with
cyanuric chloride, to hydroxyl group-containing fabrics,
to after-treat the dyeings by heating in the presence of
alkali, and to ?x the dyestuffs according to this method
to the ?bre by a chemical reaction. Compared with such
additives are, for example, surface-active substances such
as alkyl sulphates, or substances preventing the migration
known processes, the process of the invention possesses a
of the compounds applied, or other auxiliaries such as
number of advantages. The range of application of the
new process is essentially wider. In accordance with the
urea (for improving the solubility and ?xation), or inert
thickeners such as oil-in-Water emulsions, tragacanth, 40 type of ?bre material to be treated or the intended pur
starch, alginate or methyl cellulose.
pose or available apparatus, the same compound contain
The solutions or pastes are applied to the material to be
ing groups which can be alkylated, may thus be ?xed
treated, for example, by padding on the foulard or print
on the ?bre with the polyfunctional compound of the
ing, and then heating to an elevated temperature, prefer
speci?ed type most suitable in each case. This implies
ably to 40—160° C. for some time. The heating can be
not only a great variability of the intended and attain
carried out in the hot ?ue, in a steaming apparatus, on
able treatment of the fabric, but also a great variety of
heated rollers or by introducing the material into hot con
?xing conditions, for example of the temperature or con
centrated salt baths, either separately or also consecu~
centration of the acid-binding agent. Whilst with hither
tively in any sequence.
to known methods, for example, every individual dye
When using a padding or dyeing liquor without an
acid-binding agent, the dry material is subsequently passed
through an alkaline solution to which sodium chloride or
Glauber’s salt has been added. The addition of salt
diminishes the migration of the applied compounds from
the ?bre.
stuff must carry the reactive groups required for ?xation
and reacting With the ?bre, the present process enables a
whole range of dyestutls or compounds of textile ?nish
ing to be ?xed with a single polyfunctional reactive com
pound. Since these compounds with reactive groups are
naturally very sensitive to various reagents and can be
After ?xation, the treated material is rinsed hot and, it
required by the intended use of the material, ?nally
soaped, insuf?ciently ?xed residues of the applied com
produced only by especially suitable methods and also
with the observation of special instruction, the process
pounds thus being removed. Fixations of dyestuffs, hy
drophobing agents, optical brightening agents and the like
be applied in an essentially more simple and also a con
siderably safer manner. In some cases, completely new
are thus obtained which are excellently fast to wetting.
For the printing of hydroxyl group-containing materials
ways of application are disclosed. Thus, for example,
compounds containing groups which can be alkylated,
there is used a printing paste consisting of a solution of
the mixture to be applied, a thickener such as sodium algi~
mate, and an acid-binding compound, i.e. a compound
having an alkaline reaction or splitting off alkali on heat
ing such as sodium carbonate, potassium carbonate or
conditions which would exclude the presence of reactive
groups capable of reacting with the ?bre; the material may
according to the invention enables these compounds to
may now be applied to the material to be treated under
then be after-treated with the polyfunctional compound
under optimum ?xing conditions. This process is particu
sodium bicarbonate, and the printed material is then
larly suitable for the use of compounds of high molecular
rinsed and ?nally soaped, if desired.
which are capable of penetrating into the ?bre only
A modi?cation of the present process consists in that 70 weight
at
high
temperatures.
the starting components are not applied to the material
The
following
examples are given for the purpose of
as a mixture, but that the compound with a group which
illustrating the invention.
can be alkylated is applied ?rst and that the material
thus treated is then after-treated with a polyfunctional
compound of the speci?ed kind. A cotton fabric, may 75
Example 1
2 g. of the dyestuff obtainable by coupling diazotized
3,066,005
5
.
.
3-aminobenzyl-methylamine with 1-(3'-sulphophenyl)-3
6
,
Example 6
methylpyrazolone- (5) are dissolved in 100 ml. of water
,
‘
2 g. of the dyestuff used in Example 1 are dissolved
in 100 ml. of water with the addition of 3.2 g. of sodium
hydroxide, 0.3 g. of Turkey-red oil, 10 g. of urea and
6 g. of the reaction product from 1 mol of 1,5-diamino~
with the addition of 3.2 g. of sodium hydroxide, 0.3 g. of .
Turkey-red oil, 10 g. of urea and 28 g. of the reaction
product from 1 mol of naphthalene-1,3,6-trisulphochloride UK
and 3 mols of the sulphuric acid ester of ,B-hydroxyethyl
naphthalene-3,7-disulphonic acid and 4 mols of epichlor-v
amine. The solution is padded onto calico and the im
hydrin which is subsequently converted into the tetra
pregnated fabric is heated to 140° C. for 10 minutes.
epoxide. The solution is padded onto calico and the
The material is then rinsed and boiled with soap. A yel
impregnated fabric heated to 140° C. for 10 minutes.
low dyeing is thus obtained which is very fast to wetting. 10 The fabric is then rinsed and boiled with soap. A yel
low dyeing is thus obtained which is very fast to wetting.
Example 2
Example 7
A solution of 2 g. of the dyestu?’ used in Example 1
in 33 g. of water and 4 g. of sodium hydroxide solution
(38° Be.) is stirred, after the addition of 10 g. of urea and
8 g. of the reaction product from 1 mol of naphhtalene
2 g. of the dyestu? used in Example 3 are dissolved
in 100 ml. of water with the addition of 3.2 g. of sodium
hydroxide, 0.3 g. of Turkey-red oil, 10 g. of urea and
6 g. of the reaction product from 1,5-diaminonaphthalene~
1,3,6-trisulphochloride and 3 mols of the sulphuric acid
ester of ,B-hydroxyethylamine, into 50 g. of alginate thick
ening containing, 30 g. of dry substance per kilogram.
Calico printed with this printing paste is dried at 80° C.
and the print is developed within 10 minutes by subse
3,7-disulphonic acid and epichlorhydrin used in Example,
6. The solution is padded onto calico and the impreg-‘
nated fabric is heated to 140° C. for 10 minutes. The
fabric is then rinsed and boiled with soap. An orange
dyeing is thus obtained which is very fast to wetting.
quent heating to 140° C. After rinsing and boiling with
soap, a yellow print of very good fastness to wetting is
obtained.
Example 3
2 g. of the dyestuif obtainable by coupling diazotized
Example 8 ~
0.4 g. of a dyestulf mixture containing
(a) The potassium salt of nickel-phthalocyanine-(3)-‘
3-aminobenzyl-methylamine with l-hydroxynaphthalene
tetra - (sulphonyl - amino - B - hydroxyethyl - su1-_
phuric acid ester) and
4-sulphonic acid are dissolved in 100 ml. of water with
(b) The monoazo dyestulf from diazotized 1-amino-2-:
the addittion of 3.2 g. of sodium hydroxide, 0.3 g. of Tur
methoxy - benzene - 4 - (sulphonyl - amino ~ ,3 - hy
key-red oil, 10 g. of‘ urea and 6 g. of the reaction product 30
droxyethyl-sulphuric acid ester) and 1-(4'-amino
from 1 mol of naphthalene-1,3,6-trisulphochloride and 3
phenyl)-3-methyl-pyrazolone-(5)
'
mols of the sulphuric acid ester of B-hydroxyethylamine.
The solution is padded onto calico and the impregnated
in molar proportions, is dissolved in 10 ml. of a ?xing
fabric is heated to 140° C. for 10 minutes. The fabric is
then rinsed and boiled with soap. An orange dyeing is
solution containing per litre 100 g. of urea, 25 m1. of cone.
sodium hydroxide and 5 ml. of Turkey-red oil, and the
dyeing material is padded with this solution. After a heat.
thus obtained which is very fast to wetting.
Example 4
treatment at 120° C. in a drying oven for about 10 min
_
utes, subsequent washing and boiling with soap, a clear
A solution of 2 g. of the dyestuff used in Example 3 in
33 g. of water and 5 g. of sodium hydroxide solution (38°
Be.) is stirred, after the addition of 10 g. of urea and 6 g.
of the reaction product from 1 mol of naphthalene-1,3,6
trisulphochloride and 3 mols of the sulphuric acid ester
deep green dyeing in high ?xing yield is obtained which is
fast to washing, boiling solvents and to light.
With 0.4 g. of a dyestuff mixture containing the above
mentioned components (a) and (b) in a molar ratio
of 1:2, there is obtained by the process of this example a
of ,B-hydroxyethylarnine, into 50 g. of alginate thickening
dyeing having the same good yield and fastness properties,
containing 30 g. of dry substance per kilogram. Calico
but a more yellowish shade, and with 0.4 g. of a dyestu?i
45
printed with this printing paste is dried at 80° C. and
mixture containing the components (a) and (b) in a molar
the print is developed Within 10 minutes by subsequent
ratio of 1:3 a still more yellowish dyeing.
heating to 140° C. After rinsing and boiling with soap,
Example 9
an orange print of very good fastness to wetting is ob
tained.
.
Example 5
50
0.4 g. of a dyestu? mixture containing
(a) The potassium salt of nickel-phthalocyanine-(3)
tetra - (sulphonylamino - B - hydroxyethyl - sulphuric
10 g. of stearylpropylenediamine-(1,3) are dissolved in
acid ester) and
100 ml. of water with addition of 10 ml. of glacial acetic
(b) The monoazo dyestu? from diazotized 1-amino-2
acid and a cotton fabric is impregnated with this solution.
methoxy - benzene - 4 - (sulphonylamino - 5 - hy
After drying at 100° C., the fabric is dipped into a solu 55
droxyethyl-sulphuric acid ester) and 1-(3'-amino
tion of 100 g. of the reaction product from 1 mol of
phenyl) -3 -methyl-pyrazolone- ( 5)
naphthalene-l,3,6-trisulphochloride and 3 mols of the
in molar proportions, is padded onto cotton or regenerated
sulphuric acid ester of ,B-hydroxyethylamine in 100 ml.
cellulose and treated according to the instructions of Ex
of water with the addition of 20 ml. of sodium hydroxide
solution (38° Be.) and 10 g. of urea, squeezed off and 60 ample 8. A dyeing is thus obtained which is fast to wash
ing, boiling, solvents and to light. The shade of the dye
heated to 140° C. for 10 minutes. After rinsing and
ing is a clear deep green. If the proportions of the com
boiling with soap, a hydrophobed fabric of good fastness
ponents (a) and (b) are varied according to Example 8,
to wetting is obtained.
'
more yellowish dyeings are likewise obtained.
‘ ’A hydrophobed fabric which is likewise distinguished
by very good fastness to wetting can be obtained if as 65
polyfunctional ?xing component the reaction product of
Example 10
4.0 g. of a dyestu? mixture containing
1 mol of naphthalene-l,3,6-trisulphochloride and 3 mols
(a) The potassium salt of nickel-phthalocyanine-(3)
of the sulphuric acid ester of N-3-aminobenzyl-N-j3-hy
tetra - (sulphonyl - amino - )8 - hydroxyethyl - sul
droxyethyl-N-methylamine, or the reaction product of
phuric acid ester) and
t
1 mol of naphthalene-1,3,6-trisulphochloride and 3 mols 70
(b) The monoazo dyestuff from diazotized 1-amino-4
of thesulphuric acid ester of N-methyl-N-?-hydroxy
ethyl-propylenediamine-( 1,3) is used.
__ The stearyl propylenediamine-( 1,3) can be replaced with
the same or equal results by other long chain aliphatic
methyl - benzene - 5 - (sulphonylamino - p - hydroxy
ethyl-sulphuric acid ester) and 1-(4'-aminophenyl)
3-methyl-pyrazolone- ( 5 )
‘ amines such as stearyl amine or N-methyl stearyl amine. 75 in molar proportions, isapplied to a fabric and treated as
3,066,005
4%.
7
described in Example 8. A clear green dyeing is thus
obtained which is fast to washing, boiling, solvents and to
light. If the proportions of the components (a) and (b)
are varied similarly to the instructions of Example 8,
Components
ratio
(0)
shade
(6)
more yellowish shades are obtained.
If the monoazo dyestuif, obtainable by coupling with
(18).-. nickclphthalocy
acid ester)—>1
(4’-arnin0
phenyl)-3‘
meth l-pyrazo
lone- 5).
niekel-phthalo
(19)..-
0.4 g. of a dyestu? mixture containing
Lamina-3,4411
chloro-benzenc—?~
(sulphonyl
amino-B-hydro
xyethyl-sul
phuric acid ester)
——>l-(3’-arnino
phenyl)-3-methyl
pyraz010nc-(5).
l-amino-3-chloro-4
methylbenzene-B
(sulphonyl
amino-B-hy
droxyethyl-sul
cyat1ine-(3)-tetra
(sulphonyl-?
hydroxycthyD
15
sulphuric acid
ester), potas
tetra - (sulphonylamino - )3 - hydroxyethyl - sulphuric
sium salt.
acid ester) and
(b) The copper complex of the monoazo dyestuff from
diazotized 1 - amino - Z-hydroxy-3-chlorobenzene-5
20
(sulphonylamino - )3 - hydroxyethyl - sulphuric
acid
ester) and l-(4’-arninophenyl)-3-methyl-pyrazolone
(5)
(20)---. niekel-phtlialo
cyanine~(3)-tetra
(sulphonyl
amino-B-hydroxy
ethyl-sulphuric
tassium salt.
(21) __ _ .
_._._do _____________ __
light.
By starting from the coppered monoazo dyestu? from
(22).-.
.____do _____________ ._
In a similar manner mixtures from the components (a)
and (b) are listed in the following table yield on fabrics of
(a)
shade
l-amino-2-carboxy
benzene-5-sul
phonyl-amino-B
hydroxyethyl-sul
phuric acid ester)
-> 1—(4’-amino
phenyD-3-methyl
1:1
dull green.
anine-(3)-tetra
(sulphonyl
amino-B-hydroxy
ethyl-sulphuric
acid ester), potas
sium salt.
(24).--
1:1
1:1
deep green.
(sulphonylamino
?-hydroxyethyl
phthalocyanine - (3) - tetra-(sulphonyl-amino-?-hydroxy
sulphuric acid
ethyl-sulphuric acid ester) as component (a) green dyeings
ester)-—>l‘(4’
aminophenyl)-3
methyl-pyrazo
lone-(S). 9
1-aminobenzene-3
___..do ............. ..
(sulphonylamino
?-hydroxyethyl
are obtained from all combinations which have a good
fastness to boiling, Washing and solvents, but are, in gen
eral, a little less fast to light.
1:1
60
sulphuric acid
methyl-pyra zo
(a) The potassium salt of nickel-phtha1ocyanine-(3)-tetra~
1one-(5 .
1-amino-2-chloro
..-_.do ............. ._
~
(17)---.
..___do ............. -.
1:1
(sulphonyl - amino - )8 - hydroxyethyl-sulphuric acid
green.
ester) and
(b) The copper complex of the monoazo dyestu? from
benzene-5-(sul
phonyl-amino-?
hydroxyethyl-sul
phuric acid ester)
—>1-(4’-amino
phcnyl)-3-methyl
pyrazolone—(5).
1-amino-2-chloro
benzene-S-(sul
phonyl-amino-?
hydroxyethyl
sulphuric acid
ester) -—>1-(3’
amino-phenyD-3
methyl~pyrazo
lone-(5).
Example 25
0.4 g. of a dyestuff mixture containing
ester)—>l-(3’
aminophenyD-B
(16).--
1:1
It is, of course, also possible to choose other propor
tions of the components (a) and (b) than those indicated
in Examples 8-24. If in these examples instead of the
nickel-phthalocyanine derivatives there is used copper
pyrazolonc- (5) ,
(15)-.-
.--._do ............. .
(4’-amiuo
phenyl)-3
methyl-pyrazo
lone-(5).
l-amino-ZA-di
rnethylbenzene-G
(sulphonyl
amiuo-?-hydroxy
ethyl-sulphuric
pyrazol0ne-(5) .
phuric acid ester)
copper complex.
l-aminobenzenc-Zi
1:1
(4’-amino- phe
nyl)-3-methyl
Do.
—)l-(3’-an1ino
phenyD-3-methyl
_____do ............. __
lone-(5).
zene-4—(sulphonyl
amino-?-hydroxy
ethyl-sulphuric
1-amino-3-nitroben
acid estcr)—>1~
copper complex.
(14)....
1:1
acid ester)—)1
pyrazolone-(?),
1-an1ino~2-carboxy
benzenc-5-(sul
phonyhamino-B
hydroxyethyl-sul
(13)...- .-..-do _____________ .-
—>l-(3’-amin0
pl1enyl)-3
nicthyl-pyrazo
lone-(5).
l—amino-3,5-di
cl1loro-benzene-4
(sulphonylamino
?-‘iydroxyethyl
methyl-pyram
.---_<lo .... ._‘ ....... _.
(b)
(12).... nickel-phthalocy-
1:1
ester)—>l(4’
amino-phenyD-3
(23)..-.
ratio
estcr)—>1—(4’
amin0-phenyD-3
rnethyl-pyrazo
lone-<5).
l-amino-3-chloro
4-rnethylbenzene
?-(sulphonyl
amino-B-hydroxy
ethyl,sulphuric—
sulphuric acid
cotton or regenerated cellulose, dyeings in the indicated 35
shades which are very fast to wetting.
Components
1:1
acid ester)
the same diazo components and l-(3’-aminophenyl)-3
methyl-pyrazolone-(S), dull green dyeings are likewise ob 30
tained which are fast to washing, boiling, solvents and to
light.
1:1
phuric acid
acid ester), po
in molar proportions, is applied to a fabric and treated as
described in Example 8. A dull green dyeing is thus ob 25
tained which are fast to washing, boiling, solvents and to
green
(sulphonyl
amino-?ehydro
xyethyl-sulphuric
sium salt.
ings are likewise obtained.
Example 11
1:1
robcnzcnc-?
acid ester), potas
By varying thereby the proportions of the components 10
(a) and (b) similarly to Example 8, more greenish dye
(a) The potassium salt of nickel-phthalocyanine-(3)
1-amino-3,4-dichlo
anine-(3)-tetra
(sulphonyl
amino-B-hydroxy
ethyl-sulphuric
1-(3'-aminophenyl)-3-methyl-pyrazolone-(5) is used as
component (b), clear green dyeings are likewise obtained
which are fast to washing, boiling, ‘solvents and to light.
diazotized l-amino - 2 - hydroxy-3-chlorobenzene-5
(sulphonyl - amino - 6 ~ hydroxyethyl-sulphuric acid
1:1
70
ester) and l-carboxy - 2 - hydroxynaphthalene-6-(sul
phonyl-aminoethylamine)
in the molar proportions 1:1, 1:2 or 1:3, is applied to a
fabric and treated according to the instructions of Ex
ample 8. Blue dyeing are thus obtained which are fast
75 to boiling, washing and solvents and the reddish tinge
3,066,005
and then rinsed and boiled with soap. A turquoise dyeing
of which increases with increasing content of the corre
sponding monoazo dyestuif. It is also possible to use other
is thus obtained very fast to wetting.
proportions than those indicated.
I-f instead of the nickel-phthalocyanine derivative there
is used the potassium salt of copper-phthalocyanine-(3)
, Similar dyeings fast to wetting are obtainable by using
as an acid-binding agent, instead of sodium hydroxide,_
tetra-(sulphonyl - amino - 5 - hydroxyethyl-sulphuric acid
gen carbonate, sodium hydrogen carbonate, trisodium
potassium carbonate, sodium carbonate, potassium-hydro
ester) as component (a), blue dyeings are likewise ob
phosphate, sodium silicate, sodium acetate or potassium
hydroxide.
tained which are fast to boiling, washing and solvents
and the reddishtinge of which increases with increasing
Similar ?xation of the dyeing is obtained when the fabric
content of the corresponding monoazo dyestulf.
10 treated with the acid binding agent is stored at 40° C.
for one hour or at higher temperatures for a shorter period
Example 26
of time.
0.4 g. of a dyestutf mixture containing
Example 29
(a) Nickel-phthalocyanine - (3) - tetra-(sulphonylamino
B-hydroxyethyl-sulphuric acid ester) potassium salt,
(b) The monoazo dyestuif from diazotized l-amino-2
A cotton fabric is impregnated with an aqueous solution
15 containing 3% of sodium hydroxide and 1% of an algi
nate thickening, squeezed off and dried. The fabric thus
treated
is then printed with a printing paste consisting of
ethyl-sulphuric acid ester) and l-(4’-aminophenyl)
2 g. of the dyestuif mentioned in Example 1
3-methylpyrazolone- (5 ) , and
(c) The copper complex of the monoazo dyestuff from 20 8 g. of the polyfunctional compound mentioned in Ex
ample l
diazotized l-arnino~2-hydroxy - 3 - chlorobenzene-S
methoxybenzene - 4 - (sulphonylamino - [3 - hydroxy
(sulphonylamino - 18 - hydroxyethyl -‘ sulphuric acid
10 g. of urea
ester) and 1 - carboxy - 2 - hydroxynaphthalene-?-B
25 g. of Water and
aminoethylsulphonamide
60 g. of alginate thickening.
in the molar propertions 1:1:1, 1:1:2 or 1:2:1, is applied 25 The printed fabric is dried at 80° C. and then heated to
140° C. for 10 minutes. It is then rinsed and boiled
with soap. A yellow print is thus obtained which is very
to a fabric and treated according to the instructions of
Example 8. Dyeings in olive-green, black-brown or olive
fast to wetting.
green shades are thus obtained which are fast to washing,
boiling and solvents. When using the potassium salt of
copper-phthalocyanine - (3) - tetra-(sulphonylamino-B-hy
30'
droxyethyl-sulphuric acid ester) as component (a), dye
Example 30
Calico is dyed in usual manner with the dyestutf ob
tainable by coupling 2 mols of diazotised 3-aminobenzyl
methylamine with 1 mol of N,N'-di-(5’-hydroxy-7'-sul
fast to washing, boiling and solvents.
phonaphthyl-[Z'] )-urea, with the addition of sodium car
Example 27
35 bonate and sodium sulphate, then rinsed and dried. The
dyed material is then impregnated with an aqueous solu
2 g. of the dyestu? obtainable by coupling diazotized
tion containing per litre 60 g. of the reaction product from
4 - aminobenzylamine with l - hydroxynaphthalene-4-su1
1 mol of naphthalene-1,3,6-trisulphochloride and 3 mol
phonic acid are dissolved in 100 ml. of Water with the
of the sulphuric acid semiester of ?-hydroxyethylamine,
addition of 2.1 g. of sodium hydroxide, 0.3 g. of Turkey
ings in similar shades are obtained which are likewise
red oil, 10 g. of urea and 6 g. of the reaction product
from 1 mol of naphthalene-1,3,6-trisu1phochloride and 3'
40
mols of the sulphuric acid semiester of N-S-aminobenzyl
N-methyl-B-hydroxyethy1amine.
.
50 g. of urea and 20 g. of sodium hydroxide. It is
squeezed off and heated to 140° C. for 10 minutes. The
fabric is then rinsed and boiled with soap. A brick-red
dyeing is thus obtained which is very ‘fast to wetting.
Example 31
The solution is padded onto calico and the impregnated
fabric is heated to 140° C. for 10 minutes. The fabric 45.
Calico is impregnated with a 10% aqueous solution
is then rinsed and ‘boiled with soap. A red dyeing is
of the reaction product from 1 mol of naphthalene
thus obtained very fast to wetting.
l,3,6-trisulphochloride and'3 mol of the sulphuric acid
If in this examplethere is used as a polyfunctional
semiester of B-hydroxyethylamine, well squeezed off and
compound 6 g. of the reaction product from 1 mol of
dried at 80° C. Onto the fabric thus treated there is
naphthalene-1,3,6-trisulphochloride and 3 mols of the sul 50 padded a solution of 20 g. of the dyestuff obtainable by
' phuric acid semiester of ?-hydroxyethylpiperazine or N
coupling diazotized 4-aminobenzylamine with 1-naphthol
?-hydroxyethyl - N - methyl-propylenediamine-(1,3), red
4-sulphonic acid, 200 g. of urea, 2 g. of Turkey-red oil
and .21 g. of sodium hydroxide in 1 litre of water, and
Example 28
the fabric is heated to 140° C. for 10 minutes. It is then
55 rinsed and boiled with soap. A red dyeing is thus ob
l g. of the dyestuff obtainable by‘ chlorination of the
tained which is very fast to wetting.
reaction product from 1 mol of copper-phthalocyanine
dyeings fast to wetting are likewise obtained.
Example 32
Calico is treated with an aqueous solution containing
(3)-trisulphochloride and 3 mol of N-B-hydroxyethyl-N
methyl-propylenediamine-(1,3) with thionyl chloride and
corresponding to the formula:
copper-phthalocyanlne-(B)-—(SO¢—NH—-CH¢~—CHr-—GH¢
.
60 per litre 60 g. of urea, 60 g. of potassium carbonate and
60 g. of the polyfunctional compound used in Example
31. The fabric is squeezed off and dried at 80° C. The
fabric is then treated with an aqueous dyestu?f solution
containing per litre 10 g. of the dyestuff used in Example
31, 60 g. of urea and 3 g. of Turkey-red oil. The fabric
is squeezed off and then heated to 140° C. for 10 minutes.
It is then rinsed and boiled with soap. A red dyeing is
thus'obtained which is very fast to wetting.
0113
_—N
\c?s
is dissolved as a hydrochloride in 200 ml. of water. Into
this solution there is stirred a solution of the dyestuif
obtainable by coupling diazotized 3~aminobenzyl-,8-hy—
droxyethylamine with 1-phenyl-3-methyl-pyrazolone-(5)
and dissolved as a hydrochloride in 60 ml. of water.
Example 33
70
The green dyestuif solution thus obtained is padded onto
calico, well squeezed off and the impregnated fabric is
0.6 g. of a dyestuif mixture containing
(a) 0.2 g. of the potassium salt of copper-phthalocy
dipped into an aqueous solution containing per litre 40 g.
amine-(3)-tris-[sulphonylamino - A - n - propyl
of sodium hydroxide and 50 g.'of urea. After renewed
squeezing, the fabric is heated to 140° C. for 10 minutes 75
ester)] and
amino-(N’,N'-bis-B-hydroxyethyl sulphuric acid
3,066,005
12
11
and dried. The material thus treated is impregnated with
(b) 0.4 g. of the monoazo dyestutf obtainable by cou
pling diazotized l-arninobenzene - 4 - sulphonic
an aqueous solution containing per litre 60 g. of the re
acid with 1-(4’-aminophenyl)~3-methyl-pyrazo
action product from 1 mol of naphthalene-1,3,6-trisul
phochloride and 3 mols of the sulphuric acid ester of
lone-(5)
is applied to a fabric and treated as described in EX- 5 13-hydroxy-ethylamine, 50 g. of urea and 20 g. of sodium
ample 8. A green dyeing is thus obtained which is
fast to washing, boiling and solvents.
hydroxide. The fabric is squeezed off, heated to 140°
C. for 5 minutes and subsequently rinsed and soaped
In a similar manner mixtures of the components (a)
at the boil. One obtains a brightened fabric having very
good fastness to wetting.
and (b) listed in the following table yield on fabrics of
native or regenerated cellulose, dyeings in the indicated 10 In the same manner the following brightening agent
can be ?xed on cotton and regenerated cellulose:
shades which are very fast to wetting.
NaOas
SO 3N3
Components
tions in
Shade
grams
((1)
(34)---
copper phthalo
cyanine~(3)
tris-[sulphonyl
S111ll10-7-I1
ropylamino
F-N
-mcthyl-N’
?lhydroxethyl
sulphuric acid
ester)], potas
sium salt.
phthalo
(35)-... copper
cyanine-(4)
25
(b), azo dyestu?
green.
— 1-(4’-amino
phenyl)-3
methyl-pyram
terials in an aqueous medium (a) at least one water
l0ne-(5) .
0.2:0.4
cyanine-(4)
tris-[sulphonyl
soluble amino-group-containing dyestu? with at least one
replaceable hydrogen atom at the amino group and (b)
dull green.
at least one compound selected from the class consist
ing of a water-soluble colored compound and a water
5 soluble colorless compound, said compound containing
at least two substituents selected from the group con
sisting of hydroxy alkyl sulfonamide sulfuric acid semi
ester, hydroxy alkyl sulfone sulfuric acid semiester and
hydroxy alkylamino sulfuric acid semiester, the alkyl
sium salt.
copper phthalo
We claim:
1. Process for the treatment of cellulose-containing
textile materials which comprises applying to these ma
bluish
l-aminobcnzene
4-sulphonic acid—>
_____do ___________ __
.___.d0 ___________ __
0.2:0.4
group having 2 to 3 carbon atoms, and (a) and (b) be
ing of different structure; subjecting the material thus
bluish
green.
treated to the action of a temperature of from 40° C. to
160° C. in the presence of an acid binding agent and
aminol-y-n
propy amino
(N’-mcthyl-N'
thus causing chemical linkage to component (a) via com
N’ -B-hydrox
ethyl sulphuric
acid ester)]
potassium salt.
(37)-... nickel phthalo
cyanine-(3)
tris-[sulphonyl
45 ponent (b) to cellulose.
2. The process of claim 1 wherein (b) is a water
yellowish
.____do ___________ _
soluble colorless compound containing at least two hy
droxy alkyl sulfonamide sulfuric acid semiester groups,
the alkyl grouping having 2 to 3 carbon atoms.
green.
amino-y- -
propylamino
(N’,N’~bis-?
hydroxethyl
sulphuric acid
estcr)], potas
3. The process of claim 1 wherein (b) is a water
sium salt.
(38)-..
nickel phthalo
sulphuric acid ester of N-3-aminobenzyl-N-?-hydroxy
ethyl-N-methylamine.
tris-[sulplionyl
amino-v-n
propylamino
(N’,N’-bis-B
hydroxcthyl
sulphuric acid
ester)], potas
(36)--.
As polyfunctional ?xing component there can be used
with similar result the reaction product from 1 mol of
naphthalene-1,3,6-trisulpl1ochloride and 3 mols of the
Propor
_-_‘_do ___________ -
0.2:0.4
green .
cyanine-(3)
tris-[sulphonyl
amino-'y-n
propylamino
(N '-methyl-N’
hydroxethyl
55
soluble color compound containing at least two hydroxy
alkyl sulfonamide sulfuric acid semiester groups, the
alkyl grouping having 2 to 3 carbon atoms.
4. Process according to claim 1 which comprises fol
lowing up the heat treatment step with treatment in a
neutral to alkaline bath.
5. Process according to claim 1 wherein the material
is ?rst treated with an aqueous solution of the com
60 ponent (a), then subsequently treated with an aqueous
sulphuric acid
ester)], potas
sium salt.
Example 39
A cotton fabric is dyed in usual manner with an opti
solution of the component (b) and then subjected to the
heat treatment step.
6. Process according to claim 1 wherein the material
is ?rst treated with an aqueous solution of component
cal bleaching agent of the formula
i
SO1Na
OH:
with the addition of soda and sodium sulphate, rinsed
gOr-NH-GHa-CHz-IIIH
on,
(b) then subsequently treated with an aqueous solution
"3,066,005
14
13
of the component (a) and then subjected to the heat
treatment step.
7. Process according to claim 1 wherein the component
(a) and the component (b) are simultaneously applied.
8. Cellulose-containing textile materials treated accord
ing to the process of claim 1.
9. Cellulose-containing textile materials treated accord
ing to the process of claim 5.
' References Cited in the ?le of this patent
UNITED STATES PATENTS
l0. Cellulose-containing textile materials treated ac 10
cording to the process of claim 6.
11. Cellulose-containing textile materials treated ac
cording to the process of claim 7.
1,741,637
1,886,480
Lilienfeld ___________ __ Dec. 31, 1929
Haller et al ____________ __ Nov. 8, 1932
2,670,265
2,678,330
2,741,532
Heyna et a1. _________ __ Feb. 23, 1954
Gorder et al. ________ __ May 11, 1954
Guthrie ____________ __ Apr. 10, 1956
2,774,691 '
Schroeder et a1. _______ __ Dec. 18, 1956
696,282
Great Britain _________ __ Aug. 26, 1953
FOREIGN PATENTS
OTHER REFERENCES
Broden et al.: Amer. Dyestuif Reporter, January 4.
15 1954, pages P6-P13.
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