~0~ ;)7C3~ -
The present invention relates to a process for dyeing synthetic
fibrous materials from organic solvents.
According to the invention there is provided a process for the
continuous dyeing of textile materials which consist of, or contain synthetic
fibers from organic solvents, wherein the said textile materials are im-
pregnated with an organic dyeing liquor, the boiling point of which does not
exceed 150C, which contains at least one dyestuff of the formula
COOR
~ N ~ N ~ N \ (1)
in which R represents alkyl from S to 8 carbon atoms, Xl and X2 each represents
hyclrogen, chlorine, bromine, lower alkyl, lower alkoxy, trifluoromethyl or
nitro, Rl represents hydrogen, chlorine, bromine, alkyl from 1 to 4 carbon
atoms, alkoxy from 1 to 4 carbon atoms, R2 represents hydrogen, chlorine,
bromine, alkyl from 1 to 4 carbon atoms, alkoxy from 1 to 4 carbon atoms,
acetylamino or benzoylamino,.R3 and R4 each represents hydrogen alkyl,
hydroxyalkyl, cyanoalkyl, alkoxyalkyl, alkylcarbonylalkyl, alkylcarbonyl-
hydroxyalkyl, alkoxycarbonyalkyl, phenyl or phenylalkyl, alkyl and alkoxy
each containing from 1 to 4 carbon atoms, and subsequently exposed to a heat
treatment.
The dyestufs of the invention are prepaTed in generally known
20. manner by diazotizing a diazo component of the general formula (2)
COOR
~ _ NH2 (2)
X2
in which R and the substituents Xl and X2 which may be linked to the benzene
~ing are deined as above, for example, with sodium nitri.te or mineral acid or
ill P
~35Q7~
with a solution of nitrosylsulfuric acid in concentrated sulfurîc acid, and
coupling it with a coupling component of the gPneral formula (3)
~1 ,'',' :.
-N ~ 3 ( )
R4
2 ~-
in which Rl, R2, R3 and R4 are defined as above, in acid to neutral, preferably
aqueous medium~ optionally by adding solvents, for example, mono or bivalent
alcohols, acetone or glacial acetic acid,~and, optionally, in the presence
of acid-binding agents, for example, sodium acetate, magnesium carbonate or
pyridine to give the dyestuffs of the general formula 1.
The dyestuffs are obtained in water-insoluble forni, they are
separatedJ for example, by filtration and freed from adhering electrolytes
by washing with water,
Instead of a homogeneous diazo componènt a mixture of two or more
diazo compon~nts may also be used. The same applies to the coupling component.
The dyestuffs to be used according to the invention dye synthetic
fiber materials from organic solvents to produce dyeings which show a high
dyestuff yield, a very goodbuild-up and excellent fastness properties,
especially very good fastness to thermofixing, washing, rubbing and light.
Another advantage of the dyestuffs to be used according to the invention is
thoir high solubility in organic solvents, for example alcohols and, in
particularJ halogenated hydrocarbons, which may allow the dyeing process to
be operated without using solubilizérs
The dyeing liquors preferably used contain the especially valuable
dyestuffs of the formula 1 mentioned above which are distinguished by an
especially high solubility in organic solvents.
Mixtures of tha dyestuffs to be used according to the invention
may sometimes provide better dyestuff yields than the individual dyestuffs
and may also sho~ a better solubility in an organic medium.
-2-
.
.. - ~, ~ .' '.
~5C~7~
As synthetic fiber materials, materials of high-molecular-weight
polyamides, polyolefins, polyacrylonitriles, polyurethanes, polyvinyl
chlorides, polyvinyl aceta~es as well as cellulose - 2 1/2-acetate and
cellulose triacetate, especially those of high-molecular-weight polyesters~
Such as polyethylene-glycol terephthalate, are used. The said textile
materials may be used in mixtures with each other or blended with natural
fibers, such as cellulosic fibers or wool.
The fibrous materials may be dyed in any processing form suitable
for a continuous dyeing method, for example as tows, combed material, yarns,
knit or woven fabrics or as non-woven articles.
The process of the invention is operated using organic solvents,
the boiling points of which do not exceed 150C under normal conditions, for
example aliphatic hydrocarbons, such as "special boiling point spirits
(cuts)" (DIN [German Industrial Standards] No. 51 631/I. 59), aliphatic
halogenated hydrocarbons, such as methylene chloride, dichloroethane, tri-
chloroethane, tetrachloroethane, dichlorofluoromethane, dichlorotetrafluoro-
ethane and octafluorocyclobutane, aromatic hydrocarbons, such as toluene and
xylene, aromatic halogenated hydrocarbons, such as chlorobenzene and fluoro-
benzene; especially suitable are trichlorofluoromethane, 1,2,2-trichloro-1,1,2-
trifluoroethane, tetrachloroethylene, trichloroethylene and l,l,l-trichloro-
ethane.
Suitable solvents are moreover, for example, alcohols, preferably
aliphatic alcohols having up to ~ carbon atoms, advantageously mixtures of
various solvents, especially suitable are, for example, mixtures of halogenated
aliphatic hydrocarbons and aliphatic alcohols.
The padding liquor is prepared by dissolving the dyestuffs in the
solvent or mixture of solvents while stirring and, where required while
heating. For this purpose, the dyestuffs may be used in various forms, for
example free from standardizing agents, as a concentration solution in a
solvent used according to the invention or in a mixture thereof or as a
16)5~7~
composition using adju~ants ~hich are soluble in solventsJ for example
oxalkylation products of fatty alcohols, alkyl-phenols, fatty acids and fatty
acid amides.
The dyestuff solutions are most advantageously applied onto the
material by padding but also by other impregnation methods, such as spraying,
slop-padding or im~ersing.
The impregna~ion operation is preferably carried out at room
temperature but it may also be performed at a lo~er or higher temperature.
Prior to the dyestuff fixation, the textile material which has been
a treated with the dyeing liquor is then preferably dried, for example by treat-
ing it with hot air, suctioning an inert gas (such as nitrogen) or air
through it or applying superheated vapors~ for example steam or solvent
vapor, or by establishing a vacuum.
Subsequently, the dyestuffs are fixed under the action of elevated
temperatures, for exa~ple by means of hot air, dry heat, steam or solvent
vapors.
The fixation temperatures depend on the melting points of the
fibers and, in the case of a padding process, they are generally in the range
of from 100 to 240C. The heat treatment may be carried out in superheated
2~ steam or in vapors of organic solvents but also with the aid of molten metals,
paraffins, waxes, oxalkylation products of alcohols or fatty acids or in
eutectic mixtures of salts, preferably by means of dry heat, i.e. according
to the so-called Thermosol process. It is also possible to carry out the
drying operation and the heat treatment in a single operation.
The solvent vapors which escape during the drying or fixing
operation are generally recovered in suitable devices and the solvents thus
recovered may again be used for the dyeing process of the invention.
After the dyestuffs have been fixed, the unfixed dyestuff portion,
if any, is removed by a suitable aftertreatment which improves the general
3~ astnes5 properties of the dyeings. This aftertreatment is preferably
~ -4-
~56:~70~ `
carried out in the same organic solvent as already used for the dyeing, but
it may also he carried out in different organic solvents or in aqueous
liquors according to known methods.
The following Examples serve to illustrate the inven~ion, -the parts
and percentages being by weight unless stated otherwise.
X A M P L E 1:
7 g of the dyestuff of the formula
CO-0-~CH2)4-CH3
Cl - ~ - N = N - ~ - N
\ CH2-CH2-CN
were dissolved in 1 Q of perchloroethylene at room temperature. ~ls liquor
was used to pad a fabric made of polyester fibers on a padding machine with
a squeezing effect of 75 % ~weight of padding liquor, calculated on the
weight of the goods).
The material was then dried on a suitable device and thermosoled
at 210C for 1 minute. A fast yellow dyeing was obtained.
The dyestuffs had been prepared as follows: 24.2 Parts of 5-chloro-
2-amino-benzoic acid amyl ester were mixed at 0 - 5C in 100 parts by volume
of glacial acetic acid while stirring. 32.4 Parts of a 40 % nitrosyl sulfuric
acid were added to that suspension at 0 - 5C and stirring was continued
at that temperature for three hours. Towards the end of the diazotization a
slight excess of nitrous acid is expected to be present.
17.4 Parts of N-ethyl-N-cyanoethyl-aniline were dissolved in 250
parts by volume of 2 N hydrochloric acid and placed in a stirring vessel.
The diazo solution of acetic acid obtained as described a~ove of 5-chloro-2-
amino-benzoic acid amyl ester was introduced dropwise to that solution of the
a~o component at 0 - 5C while stirring thoroughly. S~irring was continued
for 1 hourl the solution was diluted with water to yield 2 Q ~nd the acid
. ~ . . . . .
. . . ~ - ' . .
~alS07~
was made neutral with solid sodium acetateO At first, the dyestuff begins
to precipitate in smeary form, but it completely turns to crystalline form
upon stirring over night. The dyestuff is filtered off, washed with water
and dried in the vacuum drying cabinet at 50C. 37 Parts of a black powder
were obtained which corresponded to the dyestuff indicated in Example 1.
E X A M A-P L E 2. ~`
7 g of the dyestuff of the formula
C0-0-(CH2~7~CH
Cl - ~ - N = N ~ ~ _ N ~ CH2~C~I3 ~
\ CH2-CH2-CN .'
were dissolved in 1 ~ of methanol at room temperature. This liquor was used
10to pad a abric o polyester fibers on a padding machine, the squeezing ~`
effect being about 40 %, the fabric was dried, thermosoled for 1 minute at
210C and washed in cold methanol or about 5 minutes, A solid~ yellow
dyeing was obtained.
The dyestuff had been prepared as follows: 28.4 Parts of 5-chloro-
2-amino-benzoic acid-octyl ester were diazotized as described in Example 1
and coupled with 17.4 parts of N-ethyl-N-cyanoethyl-aniline as described in
said example.
E X A M P I. E 3:
. ____
5 g of the dyestuff of the formula
CO-O- ~CH2,) 6CH3
zaN2 ~ - N = N - ~ - N ~ 2
'1=' CH2-CH3-CN
~ll)51~7~
were dissolved in 1 ~ of a mixture of 50.5 % of 1,2,2-trifluoro~trichloroethane
and 49O5 % of methylene chloride at about 25C. This dyestuff solution was
used to pad a fabric made~of polyester fibers on a padding machine with a
squeezing effect of about 80 %, then~ the material was dried, thermosoled
for 1 minute at 210C and washed for about 5 minutes in ~he same mixture of
solvents in the cold state. A red, solid dyeing was obtained.
The dyestuff had been prepared as follows: 28.0 Parts of 5-nitro-2-
amino-benzoic acid-heptyl ester were diazotized as described in Example 1 and
coupled with 18.8 parts of N-ethyl-N-cyanoethyl-m-toluidine as described in
said example.
E X A M P L E 4:
6.5 g of the dyestuff of the formula
C~-0-(Ctl2)5-C~13
N2 ~ - N = N ~ ~ - N ~ 2 Ctl3
CH2-CH2-CN :'
were dissolved in 1 ~ of ethanol at about 30C and applied to a fabric of
polyester fibers by slop-padding. The squeezing effect was about 45 %.
After padding, the fabric was dried, thermosoled for 1 minute at 210C and
after-treated in cold ethanol for 5 minutes. An orange, solid dyeing was
obtained.
The dyestuff had been prepared as follows: 26.6 Parts of 5-nitro-
2Q 2-amino~benzoic acid hexyl ester were diazotized as described in Example 1
and coupled with 17.4 parts of N-ethyl-N-cyanoethyl-aniline as described
therein.
E X A M P L E 5:
5 g of the dyestuff of the formula
~ .
. .
~C~5~
.. ...
( 2)7 3
2~ N = 11 -~3_N~ 2 2 z
'.
.
were dissolved in 1 Q of isopropanol at about 30C. This liquor was used
to pad a fabric made of polyester fibers on a padding machine wi~h a squeezing
effect of about 40 %, the material was dried, thermosoled for 1 minute at
210C and washed in cold isopropanol for about 5 minutes. A red, solid
dyeing was obtained.
The dyestuff had been prepared as follows: 2904 Parts of 5-nitro-
2-amino~benzoic acid octyl ester were diazotized as described in Bxample 1
and coupled with 19.3 parts oE N,N-Coxethyl-n-butyl)-aniline as described in
said example.
E X A M P L E 6:
4 g of the dyestuff of the formula
C0 0 (CH2)4 3
_ N = N - ~ N ~ 2 3
~ \ CH2-CH2-cN ;~
were dissolved in 1 Q of perchloroethylene a~ room temperature. This liquor
was used to pad a fabric of polyester fibers on a padding machine with a
squeezing effect of about 80 %, the material was dried thereafter. To fix
the dyestuff, one half of the material was thermosoled for 1 minute at 215C,
the other half was steamed for about 30 minutes at 1.5 atmg. Yellow, solid
dyeings were obtained in both cases. A similar Tesult could be obtained when
l'''`';`'
.
,
7~ ~
the dyestuff wasfixedin overheated perchloroethylene steam (at about 150C
for 10 - 15 minutes) instead of water steam.
The dyestuff had been prepared as follows: 20.7 Parts of 2-amino-
benzoic acid amyl ester were diazotized as described in Example 1 and coupled
with 17.4 parts of N-ethyl-N-~yanoethyl-aniline as described in said example.
E X A M P L E 7:
__ ______ :
4 g of the dyestuff of the formula
Co-o-(cH2)7cH3
Cl - ~ - N = N - ~ ~ CH2-CH3
H2-cN
Cl CH3
were dissolved in 1 ~ o a mixture of 50 % by volume of methylene chloride
1~ and 50 % by volume of 1,2,2-trifluorotrichloroethane at room temperatureO
~is liquor was used to pad a fabric made of polyester fibers on a padding
machine with a squeezing effect of about 75 %, the material was dried and
thermosoled for 1 minute at 210C. A golden-yellow, solid dyeing was
obtained.
The dyestuff had been prepared as follows: 31.8 Parts of 2~amino-
3,5-dichloro-benzoic acid-octyl ester were diazotized as described in
Bxample 1 and coupled with 18.8 parts of N-ethyl-N-cyanoethyl-m-toluidine as
described therein.
E X A M P L E 8:
_ _ _ _ .
5 g of the dyestuff o~ the formula
C0-0-(CH2)6-CH3
N 2 ~ _ N = N - ~ ~ ~12-CH2-
\=:/ CH2-CH2-0-CO-CH3 ~, .
`"' ,
_ g _
.~........ ~ .
were dissolved in 1 ? of trichloroethylene at about 25°C. this liquor wasused to pad a fabric made of polyester fibers on a padding machine with a
squeezing effect of about 70%. After padding the material was dried and
thermosoled for 1 minute at 210°C. An orange solid dyeing was obtained.
The dyestuff had been prepared as follows: 28.0 Parts of 2-amino-
t-nitro-benzoic acid heptyl ester were diasotized as described in Example 1
and coupled with 23.2 parts of N,N-acetoxethyl-cyanoethyl)-aniline as
described in said exaple.
E X A M P L E S:
5 g of the dyestuff of the formula
<IMG>
were dissolved in 1 ? of methylene chloride at room temperatue. This liquor
was used to pad a fabric made of polyester fibers on a padding machine with a
squeezing effect of about 65%, the material was dried and thermosoled for
1 minute at 210°C. A red violet, solid dyeing was obtained.
The dyestuff had been prepared as follows: 26.6 Parts of 2-amino-
t-nitro-benzoic acid hexyl ester were diasotized as described in Example 1
and coupled with 226 parts of 3-phenyl-amino-acetanilide as described in
said exaple.
E X A M P L E S:
10 g of the dyestuff of the formula
<IMG>
-10-
~3507C99
were dissol~ed in 1 Q of 1~2,2-trifluorotrichloroe~hane at 25C. This liquor
was used to pad a fabric made of polyester fibers on a padding machine with a
squeezing effect of 75 %. After padding the material was dried, thermosoled
for 1 minute at 210C and washed for about 5 minutes in cold 1,2,2-trifluoro-
trichloroethane. A red, solid dyeing was obtained.
The dyestuff had been prepared as follows: 26.6 Parts of 2-amino-
5-nitro-benzoic acid hexyl ester were diazotized as described in Example 1
and coupled with 23.5 parts of N,N-~acetoxyethyl-n-butyl~-aniline as
described in said example.
E X A M P L E ll:
a ~
8 g of the dyestuff of the formula
CO-~-~CH2)6-CH3 ~ ;
N 2 ~ N = N ~ ~ C~l2-C~I3
2 2
were dissolved in 1 Q of perchloroethylene at room temperature. This liquor -
was used to pad a fabric made of polyester, polyamide 6, polyamide 6,6-cellulosetriacetate and cellulose 2 1/2-acetate, a yarn made of polyvinyl chloride
fibers and combed material made of polypropylene fibers on a padding machine.
The squeezing effects were within the range of 70 to 90 % depending on the
material.
Then, the textile materials were dried, steamed for 30 minutes at
2a about 1.5 atmg (PVC: 40 minutes at 102 - 103C) and after-treated in cold
perchloroethylene for about 10 minutes. Orange, solid dyeings were obtained ~;
in all cases.
The dyestuff had been prepared as follows: 26,6 Parts of 2-amino-
5-nitro-ben70ic acid hexyl ester were diazoti~ed as described in Example 1
and coupled with 17~4 parts of N-ethyl-N-cyanoethyl-aniline as indicated
therein.
-11 -
.
9 : -
E X A M P L E 12:
3 g Q~' the dyestuff of the formula
C0-O-(CH2)5-CH3
N = N ~ ~ _ N ~ 2 2 ~A)
CH2-CH2-OH
Cl
and 5 g of the dyestuff of the formula
Co-o-(cH2)4cH3
NO2 ~ - N = N - ~ ~ CH2-C~I3 (B)
~ CH2-CH2-CN
were dissolved in 1 ~ of methanol at room temperature. This liquor was used
to pad a fabric made of polyester fibers on a padding machine wi~h a
squeezing effect of about 40 %. The material was dried, ~hersoled for
1 minute at 210C and washed cold in a mixture consisting of equal parts by
volume of 1,2,2-trifluoro-trichloroethane and methylene chloride for 5
minutes. An o~ange solid dyeing was obtained.
The two dyestuffs had been prepared as follows:
A) 27.0 Parts of 2-amino-4-chloro-benzoic acid hexyl ester were diazotized
as described in Example 1 and coupled with 19.0 parts of N-cyanoe~hyl-
N-oxethyl-aniline as described therein.
B) 25.2 Parts of 2-amino-5-nitro-benzoic acid amyl ester were diazotized
as described in Example 1 and coupled with 17.4 parts of N-ethyl-N-
cyanoethyl-aniline as indicated in said example.
E ~ A M P L E 13-
.
4 g of the dyestuff of the formula
-12-
~5~7~
~ 2)6 3
¦ ~A)
NO2 ~ _ N = N ~ ~ N ~' H2 C~3
=1/ ~ CH2-CH2-CN
Br
and 4 g of the dyestuff of the formula ~ -
CH3-~CH2)4-O-CO- ~ N = N - ~ - N- CH2-CH3 (B~
CH2-CH2-CN
'
were dissolved in 1 ~ of perchloroethylene at about 25C. This liquor was
used to pad a fabric made of polyester fibers, polyamide 6, polyamide 6,6
and cellulose triacetate fibers on a padding machine. The squeezing effects
were within the range of from 65 to 80% depending on the material. After
padding, the fabrics were dried, thermosoled for 1 minute at 190C ~polyamide
and cellulose triacetate) or at 210C ~polyester) and washed for about 5
minutes in perchloroethylene in cold state. In all casesJ yellow solid
dyeings were obtained.
The two dyestuffs had been prepared as follous:
A~ 35.9 Parts of 2-amino-3-bromo-5-nitro-benzoic acid heptyl ester were
diazotized as described in Example 1 and coupled with 17.4 parts of
N-ethyl-N-cyanoethyl-aniline as described in said example.
B) 2Q.7 Parts of 4-amino-benzoic acid amyl ester were pas~ed with 60 parts
by volume of 5 N hydrochloric acid and filled with water to a total
volume of 150 parts by volume. 20 parts by volume oE 5 N sodium nitrite
solutian were slowly added dropwise at a tempera~ure of O - 2C while
thoroughly stirring. After finishing the addition of the above solution,
-13-
.
.
~05C17~
stirring was continued at 0 - 2C for 1 hour with an excess of nitrous acid.
Then, the excess of nit~ous acid was destroyed by amidosulfonic acid and the
diazo solution was filtered.
The diazo solution so obtained was added dropwise to a hydrochloric
solution of 17.4 parts of N-ethyl-N-cyanoethylaniline in the manner described
as to the coupling of Example 1 and after-treated as described in said example.
E X A M P L E 14:
10 g of ~he dyestuff of the formula
C0 (CH2)7 CH3
2 ~ - N = N - ~ ~ ~ CH2-CH2-H ~ ~
~CH2-CBr=CH2 "
:
were dissolved in 1 ~ of perchloroethylene at room temperatureO This liquor
was used to pad a blended fabric of 67 % of polyester fibers and 33 % of
cotton on a padding machine with a~squeezing effect of about 85 %, the
material was dried, thermosoled for 1 minute at 210C and washed cold for 5
minutes in perchloroethyleneO An orange, solid dyeing was obtained on the
polyester portion of the blended fabric.
The dyestuf had been prepared as follows: 2904 Parts of 2-amino-
5-nitro-benzoic acid octyl ester were diazotized as described in Example 1
and coupled with 25.6 parts of N-~-oxethyl-N-~-bromo-allyl-aniline as
described in said example.
2Q E X A M P L E 15:
__ _ _ . _ _ _
3 g of the dyestuff of the formula
c0-0-~CH2)7C~13
N = N - ~ / 2 C 3
CH -CH -CN
-14-
~s~o~ :
were dissolved in 1 9~ of l,l,l-trichloroethane at room temperature. This
dyestuff solution was used to pad a fabric made of polyester fibers on a
padding machine. The squeezing effect was about 75%, the material was dried
and thermosoled for 1 minute at 210C. A yellow, solid dyeing was obtained.
The dyestuff had been prepared as follows: 24.9 Parts of 2-amino-
benzoic acid octyl ester were diazotized as described in Example 1 and
coupled with 17.4 parts of N-ethyl-N-cyanoethyl-aniline as described in said
example.
E X A M P L E 16:
10 g of the dyestuff of the for~ula
C0-0-(CH2~7-CH3
- N = N ~ ~ N ~ CH2-CH2-CH2-CH
CH2-CH2-OH :
Cl
were dissolved in 1 9. of a mixture of 70 % by volume of perchloro-ethylene
and 30 % by volume of methanol at 25C. This liquor was used to pad a
fabric made of polyester fibers on a padding machine with a squeezing effect
of 7Q %, the material was dried, thermosoled for 1 minute at 210 C and
washed for 5 minutes in the same mixture of solvents. A yellow, solid
dyeing was obtained.
The dyestuff had been prepared as follows: 28.4 Parts of 2-amino-
4-chloro-benzoic acid octyl ester were diazotized, as described in Example 1
and coupled with 1~,3 parts of N,N-~oxethyl-n-butyl)-aniline as described
in the same example.
E X A M P L E 17:
7 g o the dyestuff of the formula
r ~ 1 5
.:' , . , , : . . :
.. . ,. . . . . . ~ ,
~ ` -
CO-O-~CH2)4 CH3
Cl ~ _ N = N - ~ ~ CH2-CH
~ .
Cl
: ,,
WeTe dissolved in 1 Q of perchloroethylene at room temperature. This liquor
was used to pad a fabric of polyester fibers on a padding machine with a
squeezing effect of about 80 %, the fabric was dried, thermosoled for 1
minute at 210C and after-treated with the same solvent in cold state for
abOut 5 minutes. A golden-yellow~ solid dyeing was obtained.
A similar result could be obtained when methanol was used instead
o perchloroethylene. In this case, the squeezing efect was about 40 %.
The dyestuff had been prepared as follows: 27.6 Parts of 2-amino-
3,5-dichlorobenzoic acid acid-amyl ester were diazotized, as described in
Example 1 and coupled with 17.4 parts of N-ethyl-N-cyanoethyl-aniline as
described in said example.
The following Table contains a list of further dyestuffs used in
accordance with the invention which yield solid dyeings on polyester fibers
in the shades indicated therein when dyed according to the prescriptions of
Examples 1 to ]7.
,
D -16-
<IMG>
-17-
<IMG>
-18-
<IMG>
-19-
<IMG>
-20-
<IMG>
-21-
