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Патент USA US3097050

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United States Patent 0
3,097,040
ICC
Patented July 9, 1963
1
2
of dyestuffs, being, for example, stilbene, perinone, peri~
dicarboxylic acid imide, nitro, triphenylmethane, phthalo
3,697,940
PROCESS FOR DYEING NITROGENOUS FIBER_S
Richard Casty, Kaiseraugst, Switzerland, assignor to Cuba
Company, Inc., Falr Lawn, NJ.
No Drawing. Filed Feb. 1, 1960, Ser. No. 5,634
Claims priority, application Switzerland Feb. 19, 1959
16 Claims. (Cl. 8-54)
cyanine dyestutfs or, above all acid, .anthraquinonc or azo
dyestulis including both metal-free and metalllferous and
metallizable monoazo and polyazo dyestulis that contain
a grouping or substituent that is capable of reacting with
the nitrogenous ?bers.
In general, particularly good
results are obtained with dyestuffs containing two or
It is known that wool can be advantageously dyed with
sulfonated copper phthalocyanines in the presence of a 10
more sulfonic acid groups.
polyglyool ether containing a basic nitrogen atom; with
Among the above reactive groups and substituents
there may be mentioned, for example, the ethylene imlde
out
group, epoxide groups, the vinyl grouping in a vinylsul
addition the resulting dyeings are as a rule un
_
even ‘and practically useless. A similar behavior is ob
tone group or in the acrylic acid radical, and above all,
served in the case of other dyestu?’s containing sulfonic
labile substituents that are easy to eliminate with en
acid groups, for example those which contain at least 15 trainment of the bond electron pair.
two sulfonic acid groups and are capable of entering a
As labile substituents capable of elimination with en
chemical bond with the ?ber, or the 1:2-chromium or
trainment of the bond electron pair there may be men
1:2-cobalt complexes of azo dyestulfs which contains sul
tioned, for example, aliphatically bound phosphoric or
fonic acid groups. The advantageous effect of the nitrog
sulfuric acid ester groups, sulfonic acid ?uoride groups,
enous assistants is, however, in general the less pro
aliphatioally bound sulfonyloxy groups and above all
nounced, the lighter the tint. More especially in the case 7 halogen atoms, more especially a mobile chlorine atom.
of ‘the socalled pastel tints even in the presence of the
These labile substituents are advantageously in the 7- or
afore-mentioned assistants the dyeings obtained are skit
,S-position of an aliphatic radical which is bound to the
tery and the textile materials are not dyed right through.
dyestuli' molecule directly or through an amino, sulfone
Furthermore, it is as a rule necessary to raise the tem 25 or sulfonamide group. Suitable groups are, for exam
perature of the dyebath from about 50° C. to the boil 7 ple, those of the composition
slowly and evenly; this is necessary to ensure that the
material is dyed evenly and right through, both in the
case of light and dark shades.
The present process enables these disadvantages to be 30
overcome substantially or even completely. According
these groups may be bifunctional in that, on one hand,
to this process nitrogenous ?bers are dyed with dyestulis
they render the dyestufi soluble in water and, on the other,
containing at least 2 groups imparting solubility in water,
they are capable of reacting with the ?brous material.
preferably sulfonic acid groups and in the presence of a
In those dyestuifs suitable for the'present process which
compound containing at least one basic nitrogen atom
contain as labile substituents halogen atoms, these mo
to which is attached at least one radial containing a poly
bile halogen atoms may also be contained in an aliphatic
glycol ether chain, and the molecule contains at least
three
acyl radical (for example in the ?-poei-tion of a propionyl
radical) or preferably in a heterocyclic system, and in
40 the last-mentioned case there are suitable dyestu?s con-
such a group, the dyeing being performed in the presence
taining a monohalogen-ated heterocyclic group, for ex
ample a monochlorinated 1:3:5-triazine radical such as
the 1:3 :5’triazine radical of the formula
of an anion-active compound that has no dyestu?' charac
(1)
as well as at least 4 carbon atoms not forming part of
ter but possesses al?nity for the nitrogenous ?bers.
The present process is suitable for dyeing nitrogenous 45
?bers that can be dyed with acid dyestuffs by the con
ventional methods, for example silk, polyamide ?bers of
e-caprolactam or of adipic acid and hexamethylenedi~
amine. The process is especially suitable for dyeing wool,
or if desired wool blended with other ?bers which, if
desired, may likewise contain nitrogen.
The present process can be carried out with any dye
N-Gl
I
X
in which X represents an alkyl, aryl, aralkyl, alkylmer
capto or arylmercapto group or more especially an un
substituted or substituted amino group or a, preferably
substituted, hydroxyl group-as well as dyestulfs con
stu? that contains at least two groups imparting solubility
taining a dichlorotriazine group or a trichloropyrimidine
in water, for instance carboxyl groups or preferably sul
or dichloropyrimidine radical.
fonic acid groups and is suitable for dyeing nitrogenous 55
Numerous dyestulfs of the speci?ed kind are known or
?bers, more especially with dyestuffs that are conven
can be manufactured by known methods, for example
tionally used for dyeing wool from an acetic acid bath,
from dyestutl components that as such contain the afore
including those of the following types:
mentioned labile substituents, or by incorporating such
(A) Dyestu?'s that contain sulfonic acid groups and are
a labile substituent or a radical containing such a labile
gapable of entering a chemical bond with hydroxylated
substitutent by a known method in the dyestulf molecule
of a previously prepared dyestu?'. In this manner, by re
bers.
(B) Sulfonated copper phthalocyanines.
(C) Dyestuffs that consist substantially of 1:2-chro
mium or l:2~cobalt complexes of azo dyestuffs and 65
contain groups imparting solubility in water.
Quite generally it may be said that the dyestuffs advan
tageously contain at least two sulfonic acid groups.
The dyestu?s de?ned under (A) above must contain
acting an azo or anthraquinone dyestufr" containing a re
active hydroxyl, mercapto or above all amino group, for
example with chloracetyl chloride, with ?-bromopro
‘ pionyl chloride or ?-chloropropionyl chloride or chloro
propionic anhydride, with cyanuric chloride or with a
primary condensation product of cyanuric chloride con
taining two chlorine atoms and, instead of the third chlo
rine atom of cyanuric chloride, an organic radical, there
at least one reactive group or a reactive substituent. In 70 are obtained valuable condensation products that still
other respects they may belong to a wide variety of classes
contain a mobile chlorine atom and are suitable for dye
3,097,040
3
4
ing by the present process. Dyestuffs suitable for use in
(c), (d) and (e), the dyestuffs F1 and F2 may in all cases
proportion of an organic sulfonyl halide, for example
para~toluenesulfonyl chloride, benzenesulfonyl chloride
present in one and the same radical. As a rule, excessive
massing of solubilizing groups, more especially sulfonic
or ethanesulfonyl chloride, or with concentrated sulfuric
acid gto11p8—~_above_ all in compounds of a relatively low
be of identical or different constitution. The groups im
the present process that contain a sulfonylated hydroxyl
parting solubility in water may take up any desired posi
group can be prepared, for example, by reacting 1 molec
tion in the dyestuffs F1 and F2; they may be present in
ular proportion of a dyestu? containing an alkoxy group,
for example a sulfonic acid-N-hydroxyalkylamide group, 5 the radical of the diazo component or of the coupling
or a ?~hydroxyalkylsulfonic acid with at least 1 molecular
component, and if desired, 2, 3 or 4 such groups maybe
‘acid or with chlorosulfonic acid, in a manner such that 10 molecular Weight-15 undesirable 136631186 thlS may reduce
the hydroxyl group is acylated.
As dyestuffs of the kind de?ned above under (B) there
the wet fastness of the dyeings. It has been found par
tlculafly adV?m?ge°u$_W11e_n 31¢ wmplex contains, for
are to be used in the present process sulfonated copper
“ample, 2 t0 4 SillfOIllc ?eld EQTOIIPS
phthalocyanines that contain, for example 2, 3 or 4 sulThe groups (zap?ble 0f formlllg m?tal °°1T1P1¢X¢5 Pres’
fonic acid groups and, if desired, further substituents 15 “it In the mOIlO?ZO fly?tll?s are Pmferably ol'?lloiol'tho
such as halogen atoms, more especially chlorine atoms, or
sulfonamide groups. There are also suitable dyestuff
dIhYdYOXYflZO gfollplngs 01' OT’KhO-hYdTOXY-OIThQ -¢=1Tb0XY
3Z0 grouPlngs, though also other complex-formlflg gI‘OuPS
mixtures, for example sulfonation mixtures the constit-
are ‘admlsslble, Such ‘as orthojhydfloxy'ortho 'ca_1'b0XY
uents of which differ as to the number of sulfonic acid
lm‘lh?x‘i' 01‘ oriho-l’ll’dmxy-oftho 'ammo?lo gmflllflngs~
groups present in them, or mixtures of sulfonated copper 20 rljhere?l'e ‘1150 sultable further dyestuffs wmamms SP1‘
phthalocyanines with other dyestuffs suitable for dyeing
fomc 391d gmupsr not ‘sovm'ed by tha above_ de?mnon
nitrogenous ?bers from an acidic dyebath, among them,
(A), (B) 0T_ (C), Preferably 212° and anthraqumone dye’
above all, those de?ned under (A) and (C) above,
stuffs of which a large variety has been used for a long
The dyestuffs de?ned under (C) are above all 1:2-
UHF“: Past 1“ ‘the dYeShOP- ,
_
chromium or cobalt complexes of azo dyestuffs, more espe- 25
rhB afore-mentloned nitrogenous compounds contain
cially monoazo dyestuffs, that is to say complexes in which
at least one bflslc mtmgfn} atom to which 15 attafihed {it
two molecular proportions of an am dyestu?, or 1 melee,
least one radical containing a glycol ether chain; this
“1m. Pmpm?on each of two different azo dyestuffs’ are
bound in complex union to one atom of chromium or
cobalt.
chain consists of at least two members of the formula
J: l
The complex may, for example, contain one 30
'"l‘“(f—o_
glifoidig/1:53P? oingiégininggzggggei;inf?r
and it can be connectedto the nitrogen atom either di
Suitable solubilizing groups are also in this case free car-
with’ or through a budge member’ for examp1e an
boxyl groups (___coo_oation) or more especially free
a] ylene group, such as the radical of the formula
sulfonic acid groups _(—SO3-cation_); however a earboxyl 35
—CHz—CHz—CH2—
group pqmclpatmg m the forfnatlori of the .ci’mglex 1S
not considered to be a group imparting solubility in wa-
The molecule of the nitrogen compound should contain
at least three groups of me formula
of imparting solubility in water. The groups imparting
_é_é_o_
ter since, in this kind of bond, it is no longer capable
solubility in water may occupy any desired position in the 40
complex. {\s a rule, it is of advantage when at least one
sulfomc acid group is present.
|
|
01- pl-efgrably three groups of the formula
When the complex con
tains a total of two groups imparting solubility in water,
_CHT_CHT_O—
and when the complex-forming metal is represented by
Furthermore, the nitrogen compound must contain at
Me and the two dyestuffs by F1 and F3 respectively, the
least 4 carbon atoms not forming part of such a group.
following possibilities exist which are shown in the follow- 45 Inter alia, it preferably contains also at least one aliphatic
ing schematic table:
or alicyclic radical with at least 8 carbon atoms, prefer
zeooo?
1-00 0H+1——SOaH
000E
I dye oontalns 2 solublllzlng groups, I dye is free from
such groups.
/
F1
(a) Mo
\
COOH
50311
F1
OOOH
/ \
(e) Me
\
Fg
S0311
/
(b) Me
Fn-COOH
F|—-SO3H
(U
Fz~S03H
SOQH
F2
F|—CO0H
(d) Me/
Fl
(e) Me
\
Fl
Fr-COOH
Both dyes contain 1 solublllzing group each __________ __
2-SO3H
Me
{Pr-803E
Especially valuable--inter alia because of their ready aoably an aliphatic radical with a chain of at least 12 carbon
cessibility~are the dyestuffs covered by the above For- 65 atoms, or an aromatic radical with an aliphatic side chain,
mulae (e) and (j) which contain two sulfonic acid groups
which is bound to the basic nitrogen atom through an
in the molecule of the dyestuff complex, or quite generally dyestuffs containing at least two sulfonic acid
aryl carbon atom.
From the foregoing it will be realised that the present
groups in the molecule of the complex, and among them,
process can be advantageously performed with the use
above all, dyestuffs in which-as is the case with the com- 70 as nitrogenous compound of the kind referred to above
of a reaction product of at least 3 molecular proportions
plexes (f)-—-two monoazo dyestuif molecules, each of
of an az?-alkylene oxide with 1 molecular proportion of
which contains at least one sulfonic acid group, are bound
an organic compound containing at least one basic pri
in complex union to one atom of chromium or cobalt.
mary or secondary amino group, or one basic tertiary
Apart from the difference between F1 and F2 which
exists as a matter of course between the compounds (a), 75 amino group and in addition an alcoholic hydroxyl group,
3,097,040
5
or of a salt thereof or of a quaternary ammonium salt
example ?ber-a?inic anti~moth preparation containing sul
derived therefrom.
fonic acid groups, or so-called Wool resist agents (immu
Products suitable for use in the present process are
nizing agents) of the kind obtained by reacting a phenol
those which are accessible by reacting 1 molecular pro
portion of an amine with at least 3, for example 3 to 20,
or thiophenol with an alkali metal sul?de or sul?te or
sul?te-formaldehyde.
molecular proportions of an alkylene oxide, for example
a product obtained by reacting: 1 mol of dodecylamine
The amounts of substances to be
added to the dyebath used in the present process may vary
Within relatively wide limits. The amount of dyestulf
depends, of course, on the desired tinctorial strength. It
is advantageous to adapt the amount of nitrogenous com
with about 6 mols of ethylene oxide, or 1 mol of oleyl
amine with 6, 8 or 16 mols of ethylene oxide, or 1 mol of
stearlyamine with 4, 8 or 16 mols of ethylene oxide, or
monoalkyl-propylenediamine, whose alkyl radical corre— 10 pound to the amount of dyestuff so that they are used at a
ratio of about 1:8 to 1:2; it is of advantage to add the
nitrogen compound in an amount equal to about 1/1; of
the amount ‘of dyestulf. At any rate, even when a light
alkyl radical is unbranched and contains 16 to 18 carbon
shade is aimed at-for which less than 1% of dyestuif
atoms, with 6 mols of ethylene oxide.
From the foregoing it ‘will be realized that nitrogen 15 calculated on the weight of the ?bers is used-the nitro
gen compound should be at least 0.25% of the weight of
compounds of the formula
sponds to the radical of the tallow fatty acids, with 8 mols
of ethylene oxide, or monoalkyl-propylenediamine, whose
(2)
the ?brous material.
The amount of ?ber~a?inic anion-active compound is
advantageously made the greater, the less dyestuff is used.
(
'-
{OI-ELAN,’
20 For very pale shades, for which 0.1% of dyestulf or even
less and about 0.5% of the nitrogenous compound is used,
it may be advantageous to add about 0.3 to 1% of the
are particularly suitable for use in the present process; in
this formula R represents a preferably unbranched ali
anion-active compound.
It is further possible to manufacture a preparation con
phatic hydrocarbon radical containing at least 12, and
preferably 16 to 22, carbon atoms; m and :1 each = 1 or 25
taining the nitrogenous compound and the anion-active
substance.
2, and p, q and r represent whole numbers, the sum
p+q+ (m~1)(r—l) being at least 3 and at most 20, at
least one of the symbols p, q or m-l being a number
greater than 1.
It ‘will further be realized that nitrogen compounds of 30
the formula
Such a stable preparation suitable for per
forming the present process contains
(a) A compound containing at least one basic nitrogen
atom to which is attached at least one radical contain
ing a polyglycol ether chain, the molecule containing at
least three groups of the formula
(3)
35
and at least 4 carbon atoms not forming part of such
a group, and
are particularly suitable for performing the present proc
(b) An anion-active substance that has no dyestu?" char
ess; in this formula R represents a preferably unbranched
aliphatic hydrocarbon radical with at least 12 and prefer
acter but possesses al?nity for the nitrogenous ?ber.
ably 16 to 22 carbon atoms, and p and q represent whole 40
In this case there are used for every part of the nitrog
enous compound advantageously 0.2 to 2 parts of the
numbers, the sum p+q being at least 3 and preferably
from 8 to 16 inclusive.
anion-active compound and, if desired, a certain amount
Instead of a compound containing free alkoxy groups
of water is added to obtain such a preparation in the
form of a mixture or solution.
there may be used as assistants in the present process acid
esters of polybasic acids, for example those of phosphoric 45
The amount of such a preparation to be used is such as
or sulfuric acid derived from said alkoxy compounds, or
to ensure the presence of about 1/2 to 2% of the two
the water-soluble salts of these esters, for example salts
assistants (taken as a whole and calculated on the weight
of alkali metals, ammonia or an amine.
of the ?brous material) in the dyebath.
The dyeing according to the present process is per
Furthermore, it is found advantageous to dye in a
formed in the presence of an anion-active compound that 50
weakly acidic medium so that the pH value of the dye
bath is about 3 to 6, preferably 4 to 5. This pH value ‘is
has no dyestulf character but possesses affinity for the
nitrogenous ?bers. It is of advantage to use a compound
containing sulfonic acid groups in which said groups are
advantageously attached to aromatic nuclei, such as ben
zene nuclei or more especially naphthalene nuclei.
As examples of suitable compounds may be mentioned:
Alkali metal sulfonates of benzene hydrocarbons having
a long aliphatic chain,
Alkali metal monosulfates of 2-alkylbenzimidazoles con
taining a higher alkyl radical, for example the sodium
salt of the monosulfonated Z-heptadecyl-N-methyl
benzimidazole,
advantageously adjusted by adding acetic acid, or if de
sired, formic or sulfuric acid. It is of further advantage
55
to add sodium sulfate to the dyebath.
In some cases it
is advantageous to adjust the desired acidity of the dye
bath by adding an ammonium salt capable of giving off
acid, for example ammonium sulfate, phosphate or
acetate.
As is conventional in dyeing nitrogenous ?bers, more
60 especially wool, the dyeing is performed at an elevated
temperature, advantageously by beginning the actual dye
ing operation at about 50 to 80° C., then raising the dye
Alkali metal sulfonates of naphthalene substituted by
bath to the boil, and continuing and ?nally terminating
lower alkyl groups, for example sodium diisobutyl
the operation at the boil. However, it has been observed
naphthalenesulfonate,
65 that even when dyeing wool by the present process it is
Sulfonated condensation products of oxyaryl compounds
not at all necessary to raise the temperature close or
of the benzene series with formaldehyde, more espe
exactly to the boiling point of the dyebath; as a rule,
cially those obtained by condensing an hydroxyaryl com
practically identical results are obtained by conducting
pound of the benzene series with formaldehyde, fol
the dyeing operation well below the boiling temperature,
70
lowed by sulfonation and a secondary condensation of
for example within a temperature range of 80 to 90° C.
the sulfonated product with formaldehyde;
Furthermore, it has surprisingly been observed that it is
of advantage to pretreat the ?brous material to be dyed,
especially good results are obtained with reaction products
more especially the wool, in a bath containing at ?rst all
of naphthalenesulfonic acids with formaldehyde.
Further suitable are products of a different kind, for 75 ingredients except the dy-estufl, that is to say the nitrog
enous polyglycol compound, the ?ber-a?’inic anion-active
3,097,040
7
8
substance and acid or an ammonium salt.
The textile
When the afore-rnentioned assistants are omitted, an un
material is pretreated in this bath at 80 to 100° C. for
15 to 30 minutes. Then-in general without coolingthe dyestuff is added in the form of an aqueous solution,
and the material is dyed at 80 to 100° C. until the dyebath is practically exhausted.
By increasing the pH value of the acidic bath after the
dyestuff has been absorbed by the material, the wet fastness of the latter to migration of the dyestul’r' can be
improved.
10
even, practically useless dyeing results.
A level dyeing is likewise obtained by the above process
with the only modi?cation that, after addition of the
dyestuff solution, the dyebath is raised to 85° C. instead
of to the boil, and dyeing is then conducted and completed
at about 85° C.
Furthermore, instead of adding to the dyebath suc
cessively the ethylene oxide adduct and the reaction procl
not of naphthalenesulfonic acid, there may be added to
Unless otherwise indicated, parts and percentages in the
following examples are by weight.
it 1 part of a preparation obtained by mixing 1 part each
of the two afore-mentioned assistants with 1 part of water.
EXAMPLE 1
mz'lI‘nhleesthylene oxide adduct is prepared in the following
100 parts of knitting wool, 3000 parts of water, 10 15
100 parts of commercial oleylarnine are mixed with 1
parts of crystalline Sodium Sulfate, 6 parts of acetic acid
part of ?nely distributed sodium and heated to 140° C.,
of 40% strength and 0.5 part of the adduct described
whereupon ethylene oxide is introduced at 135—140° C.
below of oleylamine and ethylene oxide, 30 parts of
When the ethylene oxide is being absorbed rapidly, the
crystalline sodium sulfate and 0.6 part of a reaction prodreaction temperature is lowered to 120-125“ C., and the
not of naphthalenesulfonic acid and formaldehyde are
introduction of ethylene oxide is continued until 113
heated to 80° C. A solution of 0.1 part of the dyestu? 20 parts thereof have been absorbed. The resulting reaction
of the ‘formula
product gives a practically clear solution in water.
(4 )
S0311
H0
OH_3—CO—NH-—
21
:N-
N/
§N
" \N% i -NH— Q
l
HOaS-
NH-C
S0311
in a little water is added to the dyebath ‘prepared in this
Instead of with the dyestu?‘ of the Formula 4 wool can
manner. In the course of 1/2 hour the bath is raised to 35 be dyed in the manner described above with each of the
the boil and the wool is dyed for 1 hour at the boil, then
following dyestuffs, whereby level dyeings are likewise
rinsed and dried. A light-red, very pure tint is obtained.
obtained:
(5)
-—N=N
\
0
l
(potassium salt)
Yellow.
C =N
113E
2
NH-CHz-C Ha-O-SO r-OH
N
% \
S 0 311
HO
NH—-—-G
l
l
(‘511
l
N
(e) HiCON=N
\C/
Hots
—so.n (In
01
N
(7) 01-0
H
HO
/ \
Red.
0 —HN
l
N
S 03H
H0
|
o-N
I
80311
Yellow.
%
\Cé
0
\
NH:
I
(8)
S 0 311
Blue:
N
H03
HN-
0% \C ~01
lg i
03H
0
('31
3,097,040
Copper phthnlocyanine-disulfonic acid containing 1 t0 2 —S0a—'NH—'CHz—CHaCl groups ________________ -_ Blue.
Copper phthalocyanine further substituted by two sulfonic acid groups and 2 groups of the formula
— Or—NH-CHg—O—SO:—-OH; those substituents are in positions 3, 4', 4", and 4"’.
Turquoise.
Copper phthalooyonine-dlsultonic acid containing 243 groups of the iorniula ________________________________ __
Do.
N
¢ \
-——S01—NH—GHz-CHa—-NH—-(l1N
(‘l-EN
1i
% /
H 038
‘i0]
EXAMPLE 2
15
100 parts of hard-twisted Woolen yarn are dyed in a
ample 1 of oleylamine and ethylene oxide, 0.4 part of a
condensation product of naphthalenesulfonic acid and
formaldehyde, and 0.2 part of the dyestutf described
dyebath containing: 3000 parts of water, 30 parts of
crystalline sodium sulfate, 4 parts of acetic acid of 40%
strength, 0.5 part of the ethylene oxide adduct described
below. At 50 to 80° C. 100 parts of knitting wool are
immersed in this dyebath, which is then raised to the boil
within 1/2 hour, and dyeing is performed for 1 hour at
in Example 1, 0.5 part of a condensation product of 20 the boil. The dyed wool is rinsed and dried. A level,
naphthalene-sulfonic acid and formaldehyde, and 0.2 part
of copper phthalocyanine-trisulfonic acid.
pale, bluish grey dyeing results.
The yarn is immersed in the dyebath at about 50° C.
Manufacture of the Dyestu?
which is then raised to and maintained at 85° C. for 30
41.6
parts
of
the monoazo dyestuff obtained by coupling
25
minutes, then further raised to the boil, and dyeing at the
diazotised
l-amino-2-hydroxynaphthalene-4-sulfonic
acid
boil is performed for 30 minutes.
with
l-hydroxynaphthalene
are
dissolved
in
1000
parts
of
A pale, greenish blue, level dyeing is obtained.
water and treated with 100 parts by volume of a sodium
chromesalicylate solution containing 2.85% of chromium.
EXAMPLE 3
30 The whole is refluxed for several hours, whereupon the
The method described ‘in Example 2 is used with the
metallization is complete. The chromium complex is
following modi?cation:
salted out with sodium chloride, ?ltered off and dried.
The sodium sulfate is omitted, and there are used 0.5
part of the ethylene oxide adduct, 0.2 part of the reaction
EXAMPLE 5
product of naphthalenesulfonic acid and formaldehyde, 35
The procedure used is the same as that described in
and 0.75 part of the afore-mentioned dyestuif.
Example
4, except that the chromiferous dyestutf used in
A very level turquoise dyeing is obtained. The hard
that example is replaced by one of the undermentioned
1:2-metal complexes which are accessible by the usual
methods, and level dyeings are likewise obtained.
twisted yarn is dyed right through.
EXAMPLE 4
40
In the Table A are shown 1:2-complexes in which two
A dyebath is prepared from 3000 parts of water, 10
molecular proportions of a dyestuif are bound in complex
parts of crystalline sodium sulfate, ‘6 parts of acetic acid
union to one atomic proportion of metal.
of 40% strength, ‘0.5 part of the adduct described in Ex
TABLE A.
Metal
Dyestu?
Tint
HO
OH
i
I
C-CH|
%
C0...-_ (13) 110:5-
—N=N—-C\
W0
Brown:
0
OzN
Ho|s
OIH
O0..." (19)
(|)H
-~N=N
1110,
Vioiettish
brown.
HaC—-G——CHI
(1111;
B015
|
Cr-..-_ (20)
OH
l
C—N-
—N=N——C
G1
%
\
‘
Red.
C=N
|
H|C
(|)H
Cr._,_. (21) HOQS
—SO\H
IiO
N=N
Reddlsh blue.
8,097,040
‘ TABLE A-Continued.
Metal
Dyostu?
021? 0TH
‘Tint
H?
Cr...“ (22) ®—N=N
Reddish blue.
l
C]
05H
021?
OH
G0...“ (23)
HzN
—N=N
Green.
OZN
HOaS
H03?
(|)H
HO
C0_____ (24) ON:
Violet.
1
C1
SOQH
OH
HOaS
I
OH
l
|
C-NH
Co____. (25) QN=N—C
’
1
C=N
c1
1
Reddish brown.
00011
In the following Table B are listed til-complexes in
which 1 molecule each of two different dyestulfs are
bound to one atomic proportion of metal in complex
union.
TABLE B
Metal
1st dyeszu?
(!)H
c: ...... __ H0aS—
H0
21d dyestu?
503B
—N=N
H03?
(Im
H0
Tim;
C]
ON=N
l
Blue.
01
(26)
2”
H?
or ...... __ HOaS~8 =N~8
(27)
Cl
?H
H? a“
H0=s~
N:
(21)
?H
Grey-blue.
(2s)
13,1?‘
H01? 0H
Cr ______ _. 0zN~O =N
01
H(|) ('31
-—N=N—
Bluish grey.
|
C]
80:11
(29)
01};
Cr ______ __ Hols
H(|)
—N=N
(27)
110.? (‘)H
Cl
Hf!) (‘31
®—N=N
1
Do.
O]
i
OzN
1
(30)
(27)
3,097,040
TABLE 13-Continucd
Metal
1st dyestuff
2nd dyestu?
Tint
HO
OH
l
Cr ______ __ HOIS—
HO
l
H018
l
OH
|
\
C—N~
%
N=N—O
\
-—N=N—
(MN
OzN
~01
Brown.
—C 0 011
Brown violet.
I
(1:
l
BIC
(30)
(31)
HO
H 0:8
OH
l
HO
l
Cr ______ __
HO : S
l
OH
|
I
—-N=N
C-—-N—
—N=N~-C
OaN
G1
\
‘
C=N
|
H30
(34]
(35)
(‘)H
01' ______ ._ H03S—
%
HOi
St 0 1H
(‘)H
-N=N—-
H? (Ill
®—N=N~
Grey blue.
I
(11
I
OlN
(36)
Cl
(3?)
EXAMPLE 6
30
EXAMPLE 7
Dyeing is performed as described in Example 4 or 5,
A dyebath is prepared from 3000 parts of water, 5 parts
except that the dyebath is raised to 85 ° C. instead of to the
of ammonium phosphate, 0.6 part ‘of the adduct described
boil. Level dyeings are likewise obtained.
in Example 1 of oleylamine and ethylene oxide, as well as
EXAMPLE 8
0.4 part of a condensation product of naphthalene-sulfonic 35
A dyebath is prepared from 3000 parts of water, 5 parts
acid and formaldehyde, and 100 parts of a woollen fabric
of acetic acid of 40% strength, 0.5 part of the ethylene
are immersed in it. The whole is raised to the boil within
oxide adduct described in Example 1, 0.6 part of a con
a short time and maintained at the boil for 15 to 20 min
utes. An aqueous solution of 2 pants of one of the dye‘
densation product of naphthalenesul‘fonic acid and formal
stuffs described in Examples 4 and 5 is then added to the 40 dehycle, and 0.1 part of one of the following dystuffs. At
50° C. 100 parts of wool gabardine are immersed in the
boiling dyebath, and dyeing is performed for 1 hour at
dyebath, the temperature is raised Within 1/2 hour to the
the boil.
boil, and dyeing is performed for 1 hour at the boil.
Fast, level dyeings result of a darker tint than those pro
The fabric is dyed a level tint right through.
duced as described in Examples 4 and 5.
H O HN-O C
(as) C>~N=N
?
H O as—
Ruby red.
—S 0 1H
H| C —él —C H:
C IH I
no
i
H O as
|
S 0 1H
H3O
$113
1'10
H O 35-
0|
(42)
——S 0 3H
Hi‘ ‘i
-—S 0 IE
H O as‘
|
Blue.
17
3,097,040
18
EXAMPLE 9
A dyebath is prepared from 3000 parts of water, 10
parts of crystalline sodium sulfate, 6 parts of acetic acid
of 40% strength, 0.5 part of one of the undermentioned
ethylene oxide adducts (a) to (g), 0.4 part of a con~
3. A process which comprises dyeing wool with dye
stuffs containing at least 2 HO3S-groups in the presence
of a compound of the formula
(—CH3—-CH¢—O—) p'_H
R—N/
densation product of naphthalcnesulfonic acid and form
\
(—cH,~0H,-o-J.,-H
aldehyde, and 0.2 part of one of the dyestuifs of the
in which R represents an aliphatic hydrocarbon radical
tFormulae 4, 21 or 30. At 50° C. 100 parts of knitting
containing 16 to 22 carbon atoms and p and q represent
wool are immersed in the dyebath, which is then raised
within 1/2 hour to the boil, and the wool is dyed for 1 10 whole numbers, the sum p+q being at ‘least 3 and at most
20, and in the presence of an anion-active substance that
hour at the boil, then rinsed and dried. Level dyeings
result in all cases.
has no dyestutf character but possesses affinity for the
wool.
(a) Adduct of 8 molecular proportions of ethylene oxide
4. A process which comprises dyeing wool with dye
and a mixture of arachidylamine and behenylamine.
15 stuffs containing at least 2 HOSS-groups in the presence
(b) Adduct of 12 molecular proportions of ethylene oxide
of a compound of the formula
and a mixture of arachidylamine and behenylamine.
(c) Adduct of 4 molecular proportions of ethylene oxide
and stearylamine.
(d) Adduct of 20 molecular portions of ethylene oxide
and a mixture of arachidylamine and behenylamine.
(e) Adduct of 8 molecular proportions of ethylene oxide
and a mixture containing 30% of palmitylamine, 45%
of octadecenylamine and 25% of stearylamine.
(f) Adduct of 6 molecular proportions of ethylene oxide
and a mixture of N-alkyl-propylenediamines of which
20
(—CHt—0H¢~0—-).,—H
in which R represents an aliphatic hydrocarbon radical
containing 16 to 22 carbon atoms and p and q represent
whole numbers, the sum p-I-q being at least 3 and at
most 20, and in the presence of a sulfonated condensation
product of a hydroxybenzene and ‘formaldehyde.
5. A process which comprises dyeing wool with dye
the alkyl residues contain 16 to 18 carbon atoms.
stuffs containing at least 2 Hog-groups in the presence
of a compound of the formula
and a mixture of N-alkyl-propylenediamines of which
the alkyl residues contain 16 to 18 carbon atoms.
30
EXAMPLE 10
(—oHt—oHt_o-),,—H
The method described in Example 4 is used, except
that the condensation product of naphthalenesulfonic acid
in which R represents an aliphatic hydrocarbon radical
and formaldehyde is replaced by the product that is ob
‘containing 16 to 22 carbon atoms and p and q represent
tained when a mixture of 2 molecular proportions of
whole numbers, the sum p+q being at least 3 and at most
phenol and 1 molecular proportion of paradodecylphenol
20, and in the presence of a condensation product of
is condensed with 1.75 molecular proportions of formalde
naphthalene sulfonic acid and formaldehyde.
hyde, the reaction product is sulfonated, the sulfonic acid
6. A process which comprises dyeing wool with dye
thus obtained is further condensed with formaldehyde,
stuffs containing at least two sulfonic acid groups and
and the product is neutralised with ammonia. A level
which are capable of entering a chemical bond with
dyeing is obtained.
hydroxylated ?bers in the presence of a compound of the
I nstead of the assistant prepared from phenol and para
formula
dodecylphenol there may be used a product obtained from
2 molecular porportions of phenol and 1 molecular pro
portion of paracresol or para-octylphenol.
45
What is claimed is:
(—CH:—GH:—0-—)q-H
l. A process which comprises dyeing wool with dye
in which R represents an aliphatic hydrocarbon radical
stuffs containing at least 2 ?OaS-groups in the presence
containing 16 to 22 carbon atoms and p and q represent
of a compound of the formula
whole numbers, the sum p-l-q being at least 3 and at most
50 20, and in the presence of a condensation product of
(g) Adduct of 8 molecular proportions of ethylene oxide
L
naphthalene sulfonic acid and formaldehyde.
7. A process which comprises dyeing wool with dye
j... J
stuffs containing at least two sulfonic acid groups and at
(CHPCHr-O)r—i-—H m»:
in which R represents an aliphatic hydrocarbon radical 55 least one chlorotriazine radical in the presence of a com
pound of the formula
containing at least 12 and at most 22 carbon atoms, m
and it each represent a whole number of at the most 2,
and p, q and r represent whole numbers, the sum
p+q+(m—l)(r—-l) being at least 3, at least one of the
symbols p, q and (r-l) being greater than 1, and in the 60
presence of an anion-active substance that has no dyestutf
(—(JHa—0Hr—-0—)q—H
in which R represents an aliphatic hydrocarbon radical
character but possesses a?‘inity for the Wool.
2. A process which comprises dyeing wool with dye
stuffs containing at least 2 groups imparting solubility in
containing 16 to 22 carbon atoms and p and q represent
whole numbers, the sum p+q being at least 3 and at most
20, and in the presence of a condensation product of
water in the presence of a compound of the formula
(—~C Hz-CH:—O—) 9-H
65
naphthalene sulfonic acid and formaldehyde.
8. A process which comprises dyeing wool with copper
phthalocyanines containing at least 2 sulfonic acid groups
in the presence of a compound of the formula
(-cn,-cHt-o.),.—-H
in which R represents an aliphatic hydrocarbon radical 70
R-N
containing 16 to 22 carbon atoms and p and q represent
\
(— C H:- C 112- O—) u_H
whole numbers, the sum p+q being at least 3 and at most
20, and in the presence of an anion-active substance that
in which R represents an aliphatic hydrocarbon radical
has no dyestutf character but possesses at?nity for the
containing 16 to 22 carbon atoms and p and q represent
wool.
75 whole numbers, the sum p—|-q being at least 3 and at most
3,097,040
19
20
of m and n represents a whole number, the sum
20, and in the presence of a condensation product of
naphthalene sulfonic acid and formaldehyde.
9. A process which comprises dyeing wool with 1:2
chromium complexes of azo dyestuffs, the molecule of
the chromium complex containing at least two sulfonic GI
acid groups in the presence of a compound of the formula
(- 0111-0 Hi—0—) p411
p+q+(m-1)(r-1) being at least 3, at least one of the
symbols p, q and (r—-1) being greater than 1; and (b)
an anion-active substance that has no dyestutf character
but possesses at?nity for wool.
14. A process which comprises dyeing wool with 1:2
rnetal complex dyestutf containing in its molecular struc
ture at least 2 HO3S-groups in the presence of (a) a com
pound of the formula
(—CH¢~GH=—-O—~)Q~—H
10
in which R represents an aliphatic hydrocarbon radical
containing 16 to 22 carbon atoms and p and q represent
whole numbers, the sum p-l-q being at least 3 and at most
20, and in the presence of a condensation product of
H
( HrCHreO/Pl H
naphthalene sulfonic acid and formaldehyde.
15
111-!
10. A process which comprises dyeing wool with 1:2
in which R represents an aliphatic hydrocarbon radical
cobalt complexes of azo dyestuffs, the molecule of the
containing at least 12 and at most 22 carbon atoms; each
cobalt complex containing at least two sulfonic acid
of m and n represents a whole number of at most 2; and
groups in the presence of a compound of the formula
each of p, q and r represents a whole number, the sum
20
(—C1Iz——CHg—O-—) p-——I'I
p+q+(m-—1)(r—1) being at least 3, at least one of the
symbols p, q and (r-—-1) being greater than 1; and (b)
R-—N\ (—CH1-—OHI—O-—)Q—H
an anion-active substance that has no dyestuff character
but possesses affinity for wool.
15. A process which comprises dyeing wool with an
in which R represents an aliphatic hydrocarbon radical
containing 16 to 22 carbon atoms and p and q represent 25 thraquinone dyestui’r" containing in its molecular structure
whole numbers, the sum p+q being at least 3 and at most
at least 2 HOss-groups in the presence of (a) a compound
20, and in the presence of a condensation product of
of the formula
naphthalene sulfonic acid and formaldehyde.
11. A stable preparation containing
(a) a compound of the formula
30
35 in which R represents an aliphatic hydrocarbon radical
containing at least 12 and at most 22 carbon atoms; each
cal containing at least 12 and at most 22 carbon
of m and n represents a whole number of at most 2; and
‘atoms, m and n each represent a whole number of
each of p, q and r represents a whole number, the sum
at the most 2, and p, q and r represent whole num
p—|—q+(m——1)(r—1) being at least 3, at least one of the
in which R represents an aliphatic hydrocarbon radi
bers, the sum p+q+(m—1)(r-1) being at least
3, at least one of the symbols p, q and (r-l) being
greater than 1, and
(b) an anion active substance that has no dyestuff
symbols p, q and (r-l) being greater than 1; and (b)
an anion-active substance that has no dyestut‘f character
but possesses at?nity for wool.
16. A process which comprises dyeing wool with ?ber
character but, possesses a?inity for nitrogenous ?bers.
reactive anthraquinone dyestutf containing in its molec
12. A process which comprises dyeing wool with metal 45 ular structure more than 2 Hogs-groups in the presence
free azo dyestul’r' containing in its molecular structure at
of (a) a compound of the formula
least 2 HOaS-groups in the presence of (a) a compound
of the formula
in which R represents an aliphatic hydrocarbon radical
in which R represents an aliphatic hydrocarbon radical
containing at least 12 and at most 22 carbon atoms; each
of m and n represents a whole number of at most 2; and
each of p, q and r represents a whole number, the sum
containing at least 12 and at most 22 carbon atoms‘, each
of m and n represents a whole number of at most 2', and
each of p, q and r represents a whole number, the sum
p+q+(m—l)(r—1) being at last 3, at least one of the
p+q+(m—-l)(r—l) being at least 3, at least one of the 60 symbols p, q and (r-1) being greater than 1; and (b)
an anion-active substance that has no dyestuff character
symbols p, q and (r-1) being greater than 1', and (b)
but possesses affinity for W001.
an anion-active substance that has no dyestuff character
but possesses a?inity for wool.
13. A process which comprises dyeing wool with
phthalocyanine dyestuif containing in its molecular struc
ture at least 2 HO3S-groups in the presence of (a) a com—
pound of the formula
in which R represents an aliphatic hydrocarbon radical
containing at least 12 and at most 22 carbon atoms; each
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,926,556
1,970,578
2,179,371
2,214,067
2,228,369
2,310,074
2,773,871
2,852,331
2,940,812
2,997,362
Nuesslein ____________ __ Sept. 12,
Schoeller et al _________ __ Aug. 21,
Dyer _________________ __. Nov. 7,
Petersen _____________ __ Sept. 10,
Schoeller _____________ __ Jan. 14,
Gotte _________________ __ Feb. 2,
Brassell et a1. ________ __ Dec. 11,
Youse _______________ __ Sept. 16,
Denyer et a1 __________ __ June 14,
Baumann ____________ -_ Aug. 22,
1933
1934
1939
1940
1941
1943
1956
1958
1960
1961
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