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Патент USA US3097049

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hid-97,03?
,
United States Patent 0 ” ICC
Patented July 9, 1963
1
2
?bers than can be dyed with acid dyestulfs in the usual
3,097,039
manner, for example silk, polyamide fibers of Z-capro
lactam or of adipic acid and hexamethylene diamine.
Arthur Buehler, Rheinfelden, and Richard Casty, Kaiser
Particularly advantageous results are obtained by the
augst, Switzerland, assignors to Qiba Limited, Basel, 5 present process in dyeing wool, if desired blended with
Switzerland
No Drawing Filed Man 28, 1960’ Ser_ No. 17,795
other nitrogenous or nitrogen-free ?bers. When ap
Claims priority, application Switzerland Apr. 10, 1959
plwd to polyamlde ?bers the present Process is Particu
PROCESS FGlR DYEING NITROGENOUS FBERS
5 Claims. (Cl. 8--43)
larly advantageous since these ?bers are dyed an identical
tint, and as a rule also in identical depth, as wool, where
Hitherto only two classes of metalliferous dyestuffs 10 as in the after-chroming process the tint of the unchromed
have achieved any practical importance [for dyeing nitrog-
dyestuff is generally retained on polyamide ?bers.
eIlOllS ‘?bers, more ‘especially W001, namely, 0n the One
The dyestuifs used are 1:2-chromium or 1:2-cobal-t
hand, the 1:1-chrornium complexes of monoazo dyestulfs
complex compounds of azo-dyestulfs, for example disazo
containing sulfonic acid groups and, on the other hand, the
dyestu?s or more especially monoazo dyestuffs, that is to
1:2-chromium and 1:2-cobalt complexes of azo dyestuffs, 15 say complexes in which two molecules of one azo dye
primarily monoazo dyestuffs, in ‘which the complex molstuff or one molecule each of two different azo dyestuffs
ecule (hereinafter called “the complex” for short), conare bound in complex union to one atom of chromium
tains in the two azo dyestu? molecules which participate
or cobalt respectively. The complex may contain, for
in the complex formation and may be identical or ditferexample, a disazo dyestufr’ ‘ and a monoazo dyestuff or
out, together at most a single sulfonic acid group or pref- 20 preferably two identical or different monoazo dyestuff
erably no free sulfonic acid group at all nor a free
molecules. Furthermore, the complex must contain at
carboxyl group, that is to say one that does not particileast two acid groups imparting solubility in water such
pate in the complex formation, but does contain as a
groups being, for the present purpose, free carboxyl
rule sulfonamide groups or substituents having a similar
groups (-—COO-cation) or more especially free sulfonic
action, such as sulfone groups or sulfonic acid ester 25 acid groups (—SO3-cation); such carboxyl groups as
groups.
participate in the formation of the complex do not count
On the other hand, 1:2-complexes whose molecule conas solubilizing groups since, in this kind of linkage, they
tains more than one acid group imparting solubility in
no longer produce solubility in water. The groups im
water, for example those containing two or more sulfonic
parting solubility in Water may take up any desired posi
acid groups, have hitherto been found practically useless 30 tions in the complex. As a rule it is of advantage when
as a rule. Both from a strongly acidic and a weakly
the complex contains at least one sulfonic acid group.
acidic bath they produce on Wool extremely non~uniform
When the complex contains a total of two solubilizing
and skittery dyeings as well as weak and ?at tints.
groups, and the complex-forming metal is referred to by
Useful to very valuable dyeings of any desired tinctorial
Me and the two dyestuffs by F1 and F2 respectively there
strength and satisfactory levelness and good fastness 35 are the following possibilities available shown sche
properties can be obtained by producing the aforemenmatically in the table below:
2 ~——OOOH
One dye contains 2solubilizing groups,
one dye contains no solubilizing
groups.
C O OH
/Fl
(21) Me
\Fg
Both dyes contain one solubilizing
group each.
1 —COOH+1 -—SO3H
0 O OH
/Fi
COOH
(0) Me
\Fz
Fi-—COOH
(b) Me
tioned complexes on the ?ber or in some cases during
S 03H
/Fi
80311
(9) Me
\Fa
Ill-C0011
(d) Me
Fz-COOH
2 ——SO3H
SOaH
Fr-s03H
(f) Me
F2—SO3H
Fa—-SO:H
Of special advantage are the dyestuffs mentioned under
the dyeing operation from metal-free dyestuffs and suit(e) and (f) above-among other reasons because of their
able metal-yielding agents. It is, therefore, easy to underready accessibility-—which contain in the molecule of
stand that this dyeing method, the afterchroming method 55 the dyestuff complex two sulfonic acid groups, or quite
or the single-bath chroming method, is still widely pracgenerally dyestuffs that contain in the molecule of the
ticed although it involves considerable disadvantages
complex at least two sulfonic acid groups. Special men
and dii?culties in its performance and, substantial damage
tiori deserve those dyestutfs in which, as in the complexes
to the wool cannot be avoided.
mentioned above under (1‘), two monoazo dyestutl mole~
By the present process it is ROW possible to produce 60 cules, each of which contains at least one sulfonic acid
on nitrogenous ?bers, more especially wool, with the 1:2group, are bound in complex union to one atom of chro
complexes of the aforementioned kind-which otherwise
mium or cobalt.
are unsuitable for this purpose-in a very simple manner
Apart from the obvious ‘differences between F1 and F2
perfectly level dyeings of any desired tinctorial strength.
in the above cases (a), (c), (d) and (e), the dyestuffs
In the present process for dyeing nitrogenous ?bers that 65 F1 and F2 may in all cases have the same or a different
are suitable for dyeing with acid dyestuffs the ?bers are
constitution. In other respects the position of the solubi
dyed in an aqueous vbath in the presence of a cationlizing groups in the dyestuffs F1 and F2 is as desired;
active compound with dyestuffs consisting substantially
they may be present in the radical of the diazo or cou
of 1:2-chromium or 1:2-cobalt complex compounds of
pling component, and if desired 2, 3 or 4 solubilizing
azo dyes Whose metal complex molecule contains at least 70 groups may be present in one and the same radical. Ex
cessive massing of solubilizing groups, more especially of
two acid groups imparting solubility in Water.
The present process is suitable for dyeing nitrogenous
sulfonic acid groups, is as a rule less advantageous, more
3,097,039
3
especially when a relatively low molecular Weight is in
volved, because this may impair the wet fastness of the
dyeings. The presenceof, for example, two, three or
four sulfonic acid groups in the complex has proved es
pecially advantageous.
"The metal complex ‘forming groups in the monoazo
dyestuffs are preferably ortho:0rtho’-dihydroxyazo group
4
other suitable method, such as addition of certain water
miscible organic solvents.
The dyeing according to ‘the present process is per
formed in the presence of a cation-active compound, ad
vantageously one that owes its solubility in water ex
clusively to groupings containing basic nitrogen atoms and
advantageously at least one aliphatic radical of at least
ings or ortho-hydroxy-ortho’-carboxyazo groupings. Other
8 connected carbon atoms. Particularly suitable are
complex forming groups, such as ortho-hydroxy-ortho'
quarternary ammonium compounds.
carboxymethoxy groupings ‘or ortho—hyd-roxy~ortho' 10 Among the last-mentioned compounds may be named
aminoazo groupings are likewise admissible.
more especially the compounds of the formula
In other respects the azo dyestuffs required for the
manufacture of the metal complexes may be manufac
tured in known manner ‘from known diazo and coupling
components. Incidentally, a large number of such azo 15
dyestuifs have been known as chroming dyestuffs for a
in which R1 represents a preferably unbranched aliphatic
long time past. For the manufacture of such azo ‘dye
hydrocarbon radical containing at least 12, preferably
stuffs there are suitable, for example, ortho-hydroxy
16 to 20, carbon atoms; R2, R3 and R4 represent lower
amines or ortho-carboxyamines of the benzene and
hydrocarbon radicals, such as ethyl or methyl groups, or
naphthalene series, and as coupling components hydroxy 20 two or three of these radicals together with the nitrogen
benzenes, hydroxynaphthalenes, 2:4-dihydroxyquinolines,
atom represent a hetero ring; and X represents an anion,
pyrazolones and acetoacetyla-mino benzenes capable of
for example a halogen atom such as bromine or chlorine,
coupling in vicinal position to a hydroxyl ‘group (or an
or a met-hosulfate group.
enolizable keto group).
The statement that two or three of the radicals R2, R3
In this connection the following components may be 25 and R4 together with the nitrogen atom form a hetero
mentioned:
(1) Diazo components free from groups imparting solu
bility in water (including ortho-arninocarboxy'lic acids
not containing a further solubilizing group)
(2) Diazo components containing solubilizing groups
(3) Coupling components free from solubilizing groups
(4) Coupling components containing solubilizing groups
ring is intended to mean that such a ring is composed
either of the nitrogen atom and two of these radicals
‘attached to ‘the nitrogen atom by a simple bond and also
to each other, a third radical being present in the form
30 of a lower alkyl group; or that the whole grouping
-—N
/
R2
The 1:2-complexes to be used in the present process
can likewise be manufactured in the conventional and 35
consists of a hetero ring, the nitrogen atom being linked
as such known manner from metal~free monoazo dye
through a double bond to R2/R3 and through a single
stuffs, advantageously by a method known for the manu
‘bond to R4, and R2/R3 and R4 are likewise linked to
facture of 1:2-metal complexes free from groups im
each other as is the case, for example, with the pyn'dine
parting solubility in water. For the manufacture of sym
metrical complexes, in which‘ the metal atom is bound ‘to 40 ring.
As examples of compounds of the Formula 1 may be
two identical tdyes'tuff molecules, it is advantageous to
19R,
treat dyestuif in such manner and with such metal-yield
ing ta'gerits-ésuch as alkali chromesalicylate, chromium
mentioned cetyl trimethyl ammonium bromide, cetyl pyri
dinium bromide and tetradecyl pyridinium bromide.
Likewise suitable cation-active compounds are salts, if
acetate, sodium-cobalt tartrate, cobalt acetate or cobalt
sulfate-as give direct rise to the desired complex. To 45 desired quaternary ammonium salts of basic condensa
tion products from alkylolamides of higher fatty acids and
these methods belongs the chroming with alkali metal bi
alkanolamines such, for example, as the ‘acetate of the
chromate in the presence of a reducing agent.
condensation product from 1 mol of stearic acid methylol
To manufacture asymmetrical complexes it is in gen
amide and 1 mol of triethanolamine.
eral advisable to use another method which leads to
Furthermore there may be used in the present process
unitary products and not to mixtures containing a sub
as cation-active compounds monoquaternary ammonium
stantial portion of symmetrical by-products, some of which
salts containing at least one aralkyl radical or cycloalkyl
contain no 'solubilizing group at all and are there-fore
radical or the atomic grouping of the formula
undesirable. In such a case it is advantageous to prepare
the lzl-chromium complex from one of the two dyestuffs
from which the asymmetrical lz2-complex is synthesized, 55
preferably that dyestu?f which contains solubilizingagroups
(unless both dyestuffs contain solubilizinggroups), and
in which R1 ‘and R2 represent alkyl radicals which may be
substituted or may be interrupted by hetero atoms, the
‘with the other, metal-free dyestuif. 1It should also be
alkylene radical connecting the two nitrogen atoms con
mentioned that the 1; l-complexes as Well as the 1:2 60 taining, if desired, substituents. Particularly suitable com
complexes of ortho:ortho’-dihydroxyazo dyestuffs can be
pounds are those of the formula
made not only from the ortho:ortho'-dihydroxyazo dye
(5)
R2
stuffs themselves but also from the appropriate ortho-hy
the lzl-chromium complex so formed is then reacted
droxy-ortho'-alkoxyazo dyestuffs. Accordingly ‘there may
be used for the ‘direct manufacture of Lil-complexes
more especially for the manufacture of lcl-complexes
which are subsequently'to be made into l:2~complexes—
the appropriate ortho-alkoxydiazo compounds, more es
R1—l€\.?£R3 halogene
\R4
in which R1 represents a preferably straight-chain alkyl
radical containing 12 to 18‘ carbon atoms; R2 and R3 rep
resent alkyl radicals containing one or two carbon atoms,
and R4 represents a benzyl or cyclohexyl radical which
70 may be further substituted. As relevant examples may
Under certain conditions the working up of the 1:2
be mentioned dimethylbenzyl laurylammonium chloride,
complexes may cause certain difficulties, since these com
dimethylbenzyl-stearylamrnonium chloride, dihydroxy
pounds are readily soluble in water. A complex which
ethyl benzyl lauryl ammonium chloride and dimethyl cy
for this reason does not lend itself to salting out can be
clohexyl lauryl ammonium bromide.
isolated by evaporating the reaction mixture or by an
Finally, there may be mentioned as cation-active com
pecially the'methoxy compounds, instead of the ortho
hydroxydiazo compounds.
3,097,039
5
least two quaternary nitrogen atoms and at least one, or
preferably two, higher aliphatic hydrocarbon radicals.
process it is not necessary to raise the temperature closely
or wholly to the boiling point of the dyebath. As a rule,
practically equally good results are obtained when the
These salts correspond, for example, to the general for
mula
(4)
R5
R2
I
l [
6
C., the dyebath is then raised to the boil, and dyeing is
continued and completed at the boil. It has, however,
been observed that even when dyeing wool by the present
pounds also quaternary ammonium salts that contain at
process is performed well below the boil, for example at
@ 69
a temperature between 80 and 90° C.
(x9)
To ensure that
the nitrogenous compound can act from the onset, the
10 material to be dyed can be immersed in the bath which
contains the acid, if desired sodium sulfate, as well as the
in which R and R1 each represents a higher aliphatic hy
assistant or assistants (i.e. the cation-active compound
drocarbon radical; R2 to R6 represent alkyl, cycloalkyl or
and if desired the non-ionic dispersant) at room tempera
aralky radicals which may be further substituted; Z rep
ture or at most at a moderately raised temperature,
resents an alkylene radical which may be further substia
whereupon the dyebath is heated and when it is hot an
tuted or may be interrupted by hetero atoms or functional
aqueous solution of the dyestuff is added.
groups; Z1 and Z2 are lower alkylene radicals; n=1 or 2;
If desired dyeing can be carried out continuously, for
and X represents an anion. Relevant examples are the
example by ?rst padding the material to be dyed with a
compounds of the following formulae
cold, neutral dyestuff solution and then subjecting it to
20 a short after-treatment in a hot acid bath.
The present process is also very suitable for melange
printing on worsted slubbings. The printing pastes re
quired for this purpose contain, in addition to at least one
dyestu? and one assistant of the speci?ed composition, a
25 thickener such as tragaoanth or British @1111 and it should
also contain an acid, for example acetic acid. They may
CH3
OH OH
9369
CH3
(019)
CH:
2
Ha
also contain further additives conventionally present in
In general, it is of advantage when the dyebath con
printing pastes, for example oil of turpentine, hydrotropic
tains a non-ionic dispersant in addition to the cation 35
active compounds. Particularly suitable dispersants are
polyglycol ethers of hydroxy compounds, for example of;
alkylphenols such as para-nonylphenol or para-tertiary
octylphenol or preferably of higher aliphatic alcohols,
such as lauryl, cetyl, or octadecyl alcohol; advantageously
they are produced by an additive reaction of 10 to 50
mols of ethylene oxide with 1 mol of the selected alcohol.
There may also be used polyglycol ethers derived from
substances such as urea and/ or agents that prevent reduc
tion, such as sodium nitrobenzene sulfonate.
In other respects the procedure known in melange
printing may be followed. The printed material is
steamed, for example under atmospheric pressure, for 40
to 120 minutes, advantageously with ‘at least one inter
ruption.
The melange prints obtained in this manner are dis
tinguished by good exhaustion of the dyestu? and very
compounds other than hydroxy compounds, ‘for example
from amides of higher fatty acids or from alkylmercaptans 45 good properties of fastness.
The Wet fastness, more especially the potting fastness
with a higher alkyl radical.
of
the dyeings obtained by the present process, can in
The present process gives valuable results both in dye
some cases be considerably increased insofar as migration
ing proper and in printing. When dyeing from an aque-:
(bleeding out) is concerned by raising the pH value of
ous bath the amounts of the substances to be added to the
dyebaths used in the present process may vary within 50 the dyebath above 6, for example by adding ammonia,
after the ?bers have absorbed the desired amount of dye
relatively wide limits. The amount of dyestuff depend-,
of course on the desired tinctorial strength.
There may
also be used mixtures of complexes of the composition
stu? from an acid bath, that is to say at a pH value
below 6.
In dyeing mixtures of nitrogeneous ?bers and cellu
speci?ed above, as well as dyestuffs of a different com-_
position in a minor amount, that is to say 11p to about 55 lose ?bers, for example so-called half-wool, the increased
pH value is particularly advantageous since it enables the
20% of the total amount of dyestuil used, more especially
dyeing to be performed in 2 stages in a single bath: First,
so-called shading dyestuffs. The amount of cation~active
the Wool share of the ?ber mixture is dyed as described
compound added is advantageously about 0.25% to 2%
above, the cellulose share remaining practically undyed.
of the weight of the wool. The amount of nonaionic dis
persant used is advantageously of the same order as that 60 After raising the pH value, for example with the aid of
ammonia, sodium sulfate and then a direct dyeing cotton
of the cation-active compound.
dyestuff are added, advantageously without further heat
Furthermore it is found advantageous to dye in an acidic
ing. It is of advantage to use dyestuffs that dye wool at
to at most neutral medium so that the pH value of the dye—
most only very slightly in the neighborhood of 100° C.
bath ranges from about 3 to 7, preferably from 4 to 6.
This pH value can be advantageously adjusted by adding 65 The material is then dyed until also the cellulose ?ber
displays the desired tint, for example for 1/a hour, and
acetic acid or an ammonium salt or a mixture of these
the material is then ?nished in the conventional manner.
substances. There are used, for example, 3 to 8 parts of
acetic acid of 40% strength, or 2 to 5 parts of ammonium
To improve the wet fastness of the cellulose ?ber share
sulfate or ammonium acetate, per 100‘ parts of ?ber ma
it may be of advantage to perform a known after-treat
terial. It is also of advantage to add to the dyebath an 70 ment with an agent capable of improving the wet fast
alkali metal salt, for example sodium sulfate.
As is the general practice in dyeing nitrogenous ?bers,
more especially wool, the present process is performed at
ness, for example a condensation product of dicyandia
mide and formaldehyde.
Instead of adding the dyestuif and the cation-active
an elevated temperature, for example in the following
compound
separately to the dyebath used in the present
75
manner: the actual dyeing is begun at about 50 to 80°
3,097,039
7
&
,
process, these two substances-and if desired further
Manufacture of the Dyestu?
substances, more especially the non-ionic dispersant
41.6 parts of the monoazo dyestuff prepared by coupling
tdiazotized 1—amino-2—hydroxynaphthalene-4-sulfonic acid
can be made up into stable preparations ready for use.
These preparations likewise form an object of the present
invention and are characterized in that they contain as
dyestu? predominantly 1:2-chromium or 1:2-cobalt com—
plex compounds of monazo dyestu?s in which the mole
cule of the metal complex contains at least two acid
with 2-hydroxynaphthalene are dissolved in 1000 parts. of
water and mixed With 100 parts by volume of a sodium
chromsalicylate solution containing 2.85% of chromium.
Re?uxing for several hours completes the metalliza-tion.
The chromium complex is salted out with sodium chloride,
?ltered oil and dried.
groups imparting solubility in water, as well as a cation
active compound and, if desired, a non-ionic dispersant. 10
These preparations can be made by mixing the dye
stu? complex with the cation-active compound and, if
desired, the dispersant, or by evaporating or atomizing
EXAMPLE 2
The process described in Example 1 is carried out with
the use of the chromium complex described below. This
a solution of suspension which contains the dyestuff and
the assistant or assistants.
15 procedure yields a level, red dyeing, Whereas when the
same procedure is followed, except that the assistants
Unless otherwise indicated, parts and percentages in
mentioned are omitted, a more yellowish, skittery ‘dyeing
the following examples are by weight:
is obtained.
EXAMPLE 1
The chromium complex is prepared in the following
manner:
100 parts of knitting wool are immersed at 50 to 80° 20
A solution of 51.0 parts of the dyestu'?? prepared by
C. in a dyebath containing 3000 parts of water, 10
parts of crystalline sodium sulfate, 6 parts of acetic acid
coupling diazotized 4-chloro-2-amino-l-hydroxybenzene
é-sulfonic acid with 1~phenyl-3-methyl-5-pyraZolone-4'
of 40% strength, 1 part of cetyl trimethyl ammonium
sulfonic acid in 750 parts of water is rendered just slightly
bromide, 2 parts of the adduct from 1 mol of octadecyl
alcohol and 35 mols of ethylene oxide, and 2 parts of 25 alkaline to phenolphthalein with sodium hydroxide. 93
parts by volume of a sodium chromsalicylate solution con
the dyestu? described below. In the course of 1/2 hour
taining 2.85% of chromium are added, and the mixture
the bath is raised to the boil and the wool is then dyed
is stirred under re?ux until the parent dyestu? can no
for one hour at the boil, rinsed and dried. A level blue
longer be detected. The deep-red solution is neutralized
dyeing is obtained. When the cetyl trimethyl ammonium
bromide is omitted, a very skittery, slightly greyish, prac 30 with acetic acid and evaporated to dryness.
tically useless dyeing is obtained.
When instead of the
EXAMPLE 3
dyestuit described below the 1:2-chromium complex is
used which has been obtained in identical manner from
The process described in Example 1 is performed but
instead of the chrorniferous dyestuffs used in that example
the monoazo dyestuif of diazotized 1-amino-2-hydroXy
naphthalene-4-sulfonic acid and l-hydroxynaphthalene, a 35 one of the undermentioned 1:2-metal complexes obtain
able in the conventional manner is used, whereby level
level blue dyeing is likewise obtained. After immersion
dyeings
are likewise obtained.
of the Wool the temperature of the dyebath can. then be
‘ In the 1:2-complexes listed in Table A, 'two molecules
raised only to 85° C. instead of the boil and dyeing can
of the same dyestutf are bound in complex union to'o'ne
be continued at this temperature for one hour.
40 atom of metal.
TABLE A
Metal
Dyestuff
.
‘Tint on
wool
'
HOaS
1____ Or ____ _.
no
OH
é
®—N=N~O<
I
01
'
HO3S
'
>Red.
C=N'
I
CHa
HO
OH
l
%
2.“. O0 ____ _.
®—N=N—C \
|
01
'
C:
I
'Brown
red.
CH3
3____
OH
I
Or ____ _.
H?
/\
7
_OH
,
Grey.
_N:N___
o1
HOsS/V
(prepared by coupling diazotized 4-ehloro-2-amino-l-i
hygroxybenzene with 2:8-dihydroxynaphthalene-6~sulfonic
301
HO
1
OH
4..-- Cr ____ __ H038
—N=N—C
/
Pink.
$21“
CH3
3,097,039
11
12
EXAMPLE 4
The acetate of the composition mentioned above can
be replaced by the compound ‘of the formula
A dyebath is prepared from 5000 parts of water, 3
parts of acetic acid of 40% strength, 4 parts of the
adduct from 1 mol of octadecyl alcohol and 35 mols of
ethylene oxide, 2 parts of the acetate of the condensation
product from 1 mol of stearic acid methylolamide and 1
mol of triethanolamine, and 2 parts of the 1:2-cobalt
complex of the dyestuif of the formula
11038
OH
HO
10
A dyebath is vprepared which contains in 3000 parts
of water, 2 parts of cetyl trimethyl ammonium bromide,
1 part of the adduct from 1 mol of octadecyl alcohol
with 35 mols of ethylene oxide, 3 parts of acetic acid
of 40% strength, and 3 parts of the dyestuff No. 3 in
15 Table A.
100 parts of a polyamide fabric-are immersed in the re
100 parts of a mixture of ?bers containing
80% of wool and 20% of 'polyamide staple ?ber are im
mersed at 50° in the dyebath which is then raised to the
boil and dyeing at the boil is performed for 1 hour. A
sulting dyebath at about 50° C., the bath is raised to
95° C., and dyeing is performed for 1 hour at 95° C.
level grey dyeing is obtained.
The fabric is then rinsed and dried. A level, strong, 20
EXAMPLE 9
violet dyeing is obtained.
In an identical manner a ?abric of blended ?bers of
vThe process described in Examples 1 to 3 is performed
wool and polyamide can be dyed.
instead of with the ethylene oxide adduct described in
those examples, with an adduct from 1 mol of nonyl
EXAMPLE 5
25 phenol with 9 mols of ethylene oxide, or an adduct from
30 parts of the adduct from 35 mols of ethylene oxide
1 mol of castor oil with 40 mol-s of ethylene oxide, or
an adduct from 1 mol of tertiary dodecylmercaptan with
with 1 mol of octadecyl alcohol, and 40 parts of dextrin
8 to 10 mols of ethylene oxide.
are stirred with 400 parts of water for 15 minutes at 70°
What is claimed is:
C. :and the clear solution is treated por-tionwise with 10
parts of the lz2-chromium complex prepared as described 30
1. A process for dyeing wool, which comprises dyeing
at the end of Example 1. A solution of 6.5 parts of
the wool in an aqueous bath in the presence of a cation
cetyl trimethyl ammonium bromide in 50 parts of water
active quaternary ammonium compound of the formula
is then vigorously stirred
The mixture, which is
now-opaque but free from sediment, is stirred on for 30
minutes at 70° C. and then ‘evaporated to dryness under 35
'vacuum. The residue is gound and there are obtained
about 85parts of a, deep-violet readily water-soluble dye
preparation which dyes wool, from an acetic acid bath
Without any additives, level blue tints.
in which R1 represents an aliphatic hydrocarbon radical
In an identical manner dye preparations of the follow 40 containing 12 to 20 carbon atoms, R2, R3 ‘and ‘R4 each
ing compositions can be made:
represent a lower alkyl radical and X represents an anion,
and in the presence of a polyglycol ether of a higher
(a)
aliphatic ‘alcohol with a dyestuif consisting’ essentially
of a 1:2-metal complex compound which compound is
10 parts of ethylene oxide adduct (seeabove)
45 selected from the group consisting of chromium and
16 parts of dextrin
cobalt compounds and contains in the molecule of the
5.5 parts of cetyl trimethyl ammonium bromide
metal complex at least two sulfonic acid groups.
5.8 parts of dyestuff No. l in Table A
2. A process for dyeing wool, which comprises dyeing
'(b)
10 parts of ethylene oxide adduct (see above)
18 parts of dextrin
5 .5 parts of cetyl trimethyl ammonium bromide
8.7 parts of dyestutf No. 3 in Table A
EXAMPLE 6
the wool in an ‘aqueous bath in the presence of cetyl tri
50 methyl ammonium bromide and the adduct from 1 mol
of octadecyl alcohol and 35 mols of ethylene oxide, with
a dyestuif consisting essentially of a 1:2-metal complex
compound which compound is selected ‘from the group
consisting of chromium and cobalt compounds and con
55 tains in the molecule of the metal complex at least two
sulfonic said groups.
100 parts ‘of wool are pretreated wat the boil for 30
3. Process for dyeing wool comprising dyeing said
minutes in a ‘bath containing 2 parts of cetyl trimethyl
wool in an aqueous bath in the presence of cation active
quaternary ammonium compound of the formula
densation product from 1 mol of stearic acid methylol 60
amide and 1 mol of trie-thanolamine. The wool is then
dyed in a fresh bath containing 0.5 part of the dyestu?
N0. 3 in Table A and 2 parts of acetic acid of 40%
strength in 3000 parts of water. A level grey dyeing is
obtained.
65
EXAMPLE 7
wherein R1 is aliphatic hydrocarbon of 12 to 20 carbons,
R2, R3 and R4 are lower alkyl, and X is anion, and in
100 parts of wool are dyed as described in Example 1
the presence of non-ionic dispersant selected from the
in a bath prepared from 3000 parts'of water, 2 par-tsof
the acetate of the condensation product from 1 mol of 70 group consisting of polyglycol ether of ( 1) hydroxy com
pounds, (2) higher fatty acid amides and (3) higher
stearic acid methylolamide and 1 mol of triethanolarniue,
alkyl mercaptans, with dyestulfs consisting essentially of
1 plant of the adduct from 1 mol of 'octadecyl alcohol
a 1:2-metal complex compound which compound is
with 35 molstof ethylene oxide, v3 parts of acetic acid of
selected from the group consisting of chromium and
40% strength, and 1 part of the dyestu? No. 3 in Table
cobalt compounds and contains in the molecule of the
A. 'A'level ‘grey dyeing‘is obtained.
75 metal complex at least two sulfonic acid groups.
ammonium bromide or 2 parts of the acetate of the con
3,097,039
13
4. A dyestuff preparation which comprises a cation
active quaternary ammonium compound of the formula
314
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,970,578
2,153,701
in which R1 is aliphatic hydrocarbon containing 12 to 20
carbons, R2, R3 and R4 are each lower alkyl and X is
an anion, a non-ionic dispersant selected from the group
consisting of polyglycol ethers of (1) hydroxy com 10
pounds, (2) higher fatty acid amides and (3) higher
alkyl mercaptans, and a dyestuff consisting of chromium
and cobalt compounds and contains in the molecule of
the metal complex at least two ‘sulfonic 'acid groups.
5. Dyestuff preparation of claim 4 wherein the non 15
ionic dispersant is polyglycol ether of .a higher ‘aliphatic
alcohol.
2,674,515
2,763,530
2,890,094
2,900,218
3,903,325
2,933,489
2,973,351
3,007,912
Schoeller et al. _______ __ Aug. 21,
Straub et a1. _________ _.. Apr. 11,
Widmer et a1. _________ __ Apr. 6,
Schuetz et al. _________ __ Sept. 18,
1934
1939
1954
1956
Tucker _______________ __ June 9, 1959
Gray ________________ __ Aug. 18,
Geigy _______________ __ Sept. 8,
Biedermann et a1. _____ __ Apr. 19,
Montmollin et al _______ __ Feb. 28,
Betta et a1. ___________ __ Nov. 7,
1959
1959
1960
1961
1961
OTHER REFERENCES
Goldsmith: Chemical Industries, March 1943, pp.
326-3 28 .
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