Note: Descriptions are shown in the official language in which they were submitted.
1055205
The present invention relates to the dyeing of polyester fabrics,
such as those made from polyethylene terephthalate fibers.
The present invention is directed at improving the dyeing of the
foregoing fibrics, or of the fibers or foils from which they are made, as well
as novel dyes for that purpose.
According to the present invention, there is provided a dyestuff
comprising at least one water-insoluble dye compound having the formula:
X Rl R2
02N ~ N=N ~ N=N ~ N
lo
in which Rl, R3 and R4 can be the same or different lower alkyl or lower
alkenyl, R2 is hydrogen, halogen, lower alkyl, lower alkoxy or lower alkenoxy,
X is hydrogen, chlorine, bromine, nitrile or nitro, and Y is hydrogen,
chlorine or bromine.
In another aspect, the invention provides a process of dyeing
a polyester fabric which comprises contacting said fabric with a dispersion
of at least one water-insoluble dye compound having the following formula:
X Rl R2
02N ~ N=N ~ N=N ~ N
~L
- 1 - q~
,,
lOS5205
wherein Rl, R3 and R4 can be the same or (iifferent lower alkyl
or lower alkenyl, R is hydrogen, halogen, lower alkyl, lower
alkoxy or lower alkenoxy, X is hydrogen, chlorine, bromine,
nitrile or nitro, and Y is hydrogen, chlorine or bromine. The
preferred lower alkyl~ lower alkenyl and lower alkoxy and
lower alkenoxy group~ each have up to four carbon atoms.
The foregoing dyes are in~oluble in water, and when
applied by conventional technique~, as~ generally referred to
in U.S. Patents 3,845,o34 and 3,772,267, generally give
particularly good dyeing, strong colors of especially good
fastne~s to light and hoat. Such dyes can be mixed together
for simultaneous dyeing,
The preferred fibers dyed pursuant to the present
invention are polyethylene terephthalate fibers, but any
polyester fiber~such as polybutylene terephthalate, poly-
ethylelle-5-sulfo-isophthalate and 1,4-dinletllylol-cyclo-
~exane terephthalate i8 also suitable for the dyeing of this
invention.
Particularly valuable in connection with the present
invention are dyes having the formulae
02N- ~ _N-N- ~ -NsN_ ~ -N II
wherein R is hydrogen or methyl or methoxy, as well as
Cl OCH3 R2
02N- ~ -N-N- ~ -N=N- ~ -N III
3 C2H5
lOSSZOS
C1 1 3 ~
O~N ~ N ~ N-N~ N~ 2 5 IV
Cl H3CO C2~5
. . . ' .
NC OCH3 R2
02N ~ _ N N ~ _ N-N ~ ._ N V
H3Co 2 5
02N OCM3 R2
~ ~ ~ ~C H
wherein R2 is hydrogen, methyl or methoxy.
The fabric-~ dyed in accordance with the present inven-
tion have their fibers in the form of filaments or twisted or
untwisted films, and can be knitted, woven or non-woven textiles,
rope, coslbed or uncombed y-rn or thread, skeins, spools or b~tts.
3.
1055205
The dyestufis o~ the present invention are
insoluble in water. They are most readily utilized in the
form oi' a~ueous dispersions wherein they are present in a
fine division with particle sizes oi 0.1 to 10 ~, and
preferably 0.5 to 2 ~. These are obtained by mixing the
dyestuffs together with liquids, preferably water, and
disintegrating the mixed dye particles, optionally in the
presence oi' suitable dispersing agents.
Suitable dispersing agents are anion-active,
examples being lignin sulfonates, alkyl or alkylaryi
sulitonates or alkylarylpolyglycol ether sulionates.
The dye particle disintegration is preferably
eiiected mechanically by milling in suitable aggregates such
as ball, bead or sand mills, roll mills, grinding or impact
mills or attrition devices.
The dyestuff dispersions are prei'erably pourable ior
most of the specii'ic embodiments oi' the present invention. The
dyestui'i' and dispersing agent content is limited, there~ore,
in these instances. Generally, the dispersions are
standardized to a dyestuf~ content of up to 30 % by weight
and a dispersing agent content oi' up to about 25 %. For
economic reasons dyestuff contents usually do not iall below
15 % by weight.
The dispersions may also contain further auxiliary
agents such as iungicides, as ior example sodium-o-phenyl-
phenolate and sodium pentachlorophenolate.
~ lOS5205
The dyestuff dispersions thus obtained may be empl~yed ~ ;
advantageQusly for the standard of printing pastes and dye baths
used according to the present invention. Special advantage~ are
obtained this way in the continuous processes, for example, where-
in the dyestuff concentration of the dye baths is maintained ~ i
substantially constant by continuous dyestuff feeding into the
running apparatus. ¦
For certain specific embodiments of the novel process,
e.g. in the charging operation, in the introduction of the dye- , ¦
stuff for tinting or in the use under special climatic conditions,
powder standardizations are preferred since their technical
properties do not change over long periods of time. These powders
contain the dyestuff, dispersing agents and other auxiliary
agents such as wetting, oxidation, preserving and dust-arresting s
agents. Such powder ~tandardizations are redispersible, i.e.
with a simple stirring into a liquid medium, preferably water,
they yield stable dyestuff dispersions wherein the dyestuff
particles have the above-stated size.
A preferred method of preparation for the pulverulent
dyestuff consists of removing the liquid from ~the above-described
liquid dye~tuff dispersions. This removal may be carried out
by means of all methods suitable for this purpose such as vacuum
drying, freeze drying, drying on roller dryers, but preferably
by spray drying.
5-
.
1055;~05
For the preparation oi the aqueous dye liquors to be
used according to the invention, the required amounts oi the
liquid or solid dyestuff standardizations are thinned with
water to such an extent that a dye-to-liquor ratio of 1:5 to
1:50 results. In addition, further dyeing auxiliary agents
such as dispersing, wetting and padding agents are generally
added to the liquors. As the wetting and dispersing agents
for the preparation of the liquors, the iollowing aré
considered: reaction products of alkylene oxides, such as
ethylene or propylene oxide, with alkylatable compounds, such
as i'atty alcohols, fatty amines, fatty acids, phenols,
alkylphenols, aromatic or aliphatic carboxylic acid amides
or lignin sulfonates, alkyl or alkylaryl suli'onates or
alkylaryl polyglycol ether suli'onates.
The preierred auxiliary padding agents are
polymeric acrylic acid derivat~ves, such as polyacrylamides
with a K value of about 120. The above-mentioned auxiliary
agents are preferably employed in quantities oi' 0.2 to 5 %
by weight, referring to the total weight of the dye liquor
or printing paste.
The amount of dyestuif used varies depending on the
circumstances, such as the required dye speed, the fiber
structure, the color type, and the desired depth of color.
However, preierable dyestuif quantities are up to 5 ~ of the
iiber weight.
1055Z05
For ~tandard uso of a weakly acid pH value,
organic acid~ may bo added such a~ lower aliphatic
carboxylio aoids~ examples of which are formic acid or
acetic acid. For ~tandardl~ation of an alkaline pl-l value,
alkali hydrogen casbonate, such as sodium or potassium
hydrogon oarbonate, is preferably used. The dyeing may take
place in variou~ manner~ inoluding the carrier proces~, the
HT procoee and tho thormosol process.
In tho carrler process t}le material to be dyed
wlth a dye liquor~ which is obtained as described above, 18
treated at 95-105C in the presence of up to 2 ~ by weight,
referring to the quantity of llquor, of a carrier, i.e. a
fixing agont, until the main quantlty of dyestuff has gono
on the matorial to be dyed, The tlme required for this
purpose i8 ad~usted to the clrcumstances of the particular
case, such a~ tho type of dye~tuff, the fibers and the
carrier, and fluctuates proferably within the limits of
15 - 120 ~inute~ Known Garriers which may be used in this
manner aro~ for oxample~ phenylphenols, halogenated
benzene~ and saliGylic aoid ester~.
In tho HT proceoe tho goods to be dyed are
treated with a dye liquor which contains no carrier but
otherwiso i~ propared as described above, in pressure-
re~istant dyoing containor~ under the vapor pres~ure of tho
dye liquor at 120-140 C, for 15 to 120 minutes and
preferably 15 to 60 minute~.
1055Z05
In the thermosol proce~ the good~ to be dyed are
padded with the dyo liquor and optionally after an inter-
mediatH drying~ are conduoted over lleated roLlers or through
a hot air or vapor stream, the dyestuff being fixed in the
fiber~ at temperatures of 180 - 220 C chiefly.
~ or printing on fabrics the dyes are preferably
compounded ln printing pastes containing the required
quantities of the liquid or redispersible solid dyestuff
standard formulatlon together with thickening agents, such
as alkali alginates, carob bean flour, starch, tragacanth
or even inorganlc gels~ and optionally further additives
such as organic acids, alkali, fixing accelerators, wetting
agents and oxidation agent~. Considered chief`ly as organic
acids are monobasic or multibasic aliphatic carboxylic acids,
such a~ formic acid, acetic acid, propionic acid, oxalic
acid, or particularly advantageously tartaric or citric acid.
A~ the alkali, sodium and potas~ium hydrogen carbonate are
preferred. Nitrobenzene derivatives, such as m_nitrobenzene
sulfonic acid, for example~ are employed advantageously for
oxidants, The thickening agents are added to the printing
pastes normally ln quantitiec of 40 - 60 g per kg printing
paste, fixing aooelerator and wetting agent in quantities
of 5 to 50 g per kg printing paste, and oxidation agent in
quantitie~ of up to 10 g per kg printlng paste.
1055Z05
The textile goods are pri~lted wit~l these printing
pastes and optionally after an interlllediate drying conducted
over heatod roller~ or through a ~tr~am of hea-ted air or
~uperheated vapor, the fixing of the dyestuff setting in the
fiber. The operation here proceeds preferably at air or roller
temperaturg~ of 150 - 220 C or at vapor temperatures of
120 - 160C,
The dyed or printed goods are washed with water,
optionally in tho presence of a watting agent, and dried.
A reductlv~ after-treatment with 0,2 ~ alkaline sodium
dithionite solution may take place for 15 minutes at 60 -
90C after the wa~hing, Subsequently it iR then again washed
with water and dried.
A further ~pecific embodiment of the dyeing
process of the pre~ent invention applied the dyestuff~ of
~ormula I to the fabrics to be dyed while the dyestuffs are
dispersed in organic ~olvents. Dye liquors 90 made generally
contain over 80 ~ by weight of an organic solvent.
Suitabla organic oolvents for this purpose
normally have a bolling point of 25 -to 150C, and
preferably 40 to 150C. Examples for such organic solvents
are, for example~ aliphatic hydrocarbons ~uch as benzine~,
aliphatic hydrocarbon halldes such as methylene chloride,
dichloroethane, trlchloroethane, tetrachloroethane, dichloro-
fluoromethano~ dichlorotetrafluoroethane and octafluoro-
cyclobutane, aromatic hydrocarbons such as toluene and
xylene, and aromatic hydrocarbon halides such as chloro-
benzene, benzotrifluoride and fluorobenzene, Particularly
suitable are
l ~
~l
` lOSS205 1, ~' ~'
. i , , ,
~ .
trichlorofluoromethane, 1,2,2-triçhloro-1,1,2-trifluoroethane, - v l
tetrachloroethylene, trichloroethylene and l,l,l-trichloroethane. i;
Particularly interesting as organic solvents are the l ¦
lower alcohols, preferably aliphatic alcohols with 1 to 4 carbon
atoms. Mixtures of various solvents are often advantageous; ,
particularly suitable, for example, are mixtures of halogenated
aliphatic hydrocarbons and aliphatic alcohols.
For the preparation of the dye liquors the dyestuffs ' -
are dissolved in th~ organic solvent or in the solvent mixture by :~
stirring, optionally with the help of heating. The dyestuffs '
may be added in vari~us forms, e.g. in a diluent-free form, or
as a conc~ntrated solution in an organic solvent or solvent mix-
ture or in a prepared form using solvent-soluble auxiliary agents
such as ethoxylated derivatives of fatty alcohols, alkyl phenols, ~
fatty acids and fatty acid amides. The liquid and pulverulent 7
dyestuff standardizations employed for the preparation of aqueous
dye liquors may also be added to the organic solvents.~ ~
The dye liquors based on organic solvents may also 1 ¦
contain up to 10% Water. Thi~ additive can considerably favor ' -¦~
the dye absorption by the fabrics being dyed. ¦ -~
The dyeing of fabrics in liquors based on organic
solvents may take place in various ways.
Thus the ~abrics padded with the dye liquors are heated
at normal or elevated pressure to temperatures which are between
the normal boiling point of the dye liquor and preferably 140C `~
until the main portion of the dyestuff is absorbed on the fabric'sl -,
fibers.
i `,
10 .
~osszo5
For this purpose different dyeing times may be used,
depending on the circumstances of the particular case, such as
the type of dyestuff, the fibers and selected temperature, In
view of the mana~eability of the dyeing process on the one hand
and effici~ncy on the other hand, dyeing times of 15-120 minutes
are preferred.
The dyeing can be carried out continuously, in which
event textile materials may be impregnated with the dye liquors
and subsequently, optionally after an intermediate drying, are
subjected to a suitable fixing process. ?
The applicatiGn of the dye liquors to textile materials
takes place most suitably by padding but may also take place by
other impregnation processes such as spra~ing,
dipping and the like. The application of the dye liquor as by
impregnation is preferably at room temperature, but it is possibl-
to work at lower or higher temperatures.
The textile treated with the dye liquor is preferably
dried prior to the dyestuff fixing, Drying may be, for example,
by warm air, by the forcing through of an inert gas (such as
nitrogen) or air, or by using superheated vapors, such as water
vapor or solvent vapor, or by the use of vacuum.
The dyestuffs can then be fixed by the use of elevated
temperatures, e.g. by hot air, dry heat, or water or solvent
vapor. The fixing temperatures depend on the fiber and generally
are between 100 and 240C. The heat treatment may take place in
superheated water vapor or in vapors of organic solvents, in
molten metals, paraffins or other waxes, ethoxylated derivatives
i
j.
11. '
.
~,
1055;~05
o~ alcohols or ~atty acids, or in eutectic salt mixtures.
However, pre~erred is the ~ixing by dry heat, i. e. in
accordance with the co-called thermosol process.
It is also possible to efiect drying and heat
treatment in one operation. The solvent vapors evolved in
drying or ~ixing can be reclaimed in suitable apparatus, and
the solvents thus recovered may then be used again ior the
preparation o~ new dye liquors.
The dyeing o~ the present invention may also take
place by circulating a dye solvent through a quantity of the
dyestuf~ and subsequently into contact with the ~abrics,
where the dyestui~ is released from the deposit and absorbed
by the fabric. The solvent can then be recycled back to
dyestuff.
After ~ixing o~ the dyestui'~s, the unfixed dyestu~f
portion is optionally removed by a suitable post-treatment,
inasmuch as this i~creases the service ~astnesses o~ the
dyeing. This post-treatment is pre~erably carried out in the
same organic solvent used for dyeing but may also take place
in other organic solvents or in aqueous liquors.
Features o~ the present invention are that deep
blue-violet; to blue-gray dyeings and prints are obtained with
very good coloristic properties, such as color strength,
build-up capacity, particularly good fastness to light and
sublimation, high pH-stability, and very good i?astness to wet
processing, particularly in the 95C wash, in the peroxide
wash, in the chlorine wash, good resistance to alkaline and
acid prespiration, ~astnesses to solvents and to dry
cleaning, to nitric oxide and exhaust gas, boiling soda,
peroxide bleach and hypochlorite, both light and heavy.
12
1055205 - 1'
In the dyeing and printing of blends of polyesters with 5;
wool or cotton, the natural fibers are only slightly colored by
the dyes of the present invention. ¦
The dyestuffs of the present invention are easily pre-
pared from p-nitro-pl-aminoazobenzenes of the Formula
X QR`
2~ ~ N ~ 2 VII
which in turn are prepared as described in U. S. Patent 3,845,034.
The nitro-aminozaobenzene is diazotized and the diazonium compound
obtained is coupled to an aniline derivative of the Formula
~2
R VIII
~4
wherein radicals X, Y and Rl through R4 have the above-stated
meanings.
- The diazotation of the aminoazobenzenes of Formula VII
takes place in the conventional manner by the action of nitrous
acid or of compounds that form nitrous acid. For example the
nitro-aminoazobenzenes may be dissolved in sulfuric acid or in
lower aliphatic carboxylic acids, such as acetic acid or propionici
acid, for example, and diazotized at 0 to 30C by the addition of
nitrosyl sulfuric acid. The coupling is carried out in an acid,
aqueous medium at temperatures of 0 to 30C, preferably 0 to 5C.
For a completion of the coupling reaction it may be suitable to J
buffer the p~ value of the coupling deposit toward the end of the
reaction by the addition of alkali, such as sodium acetate, to a
value of S.
1055Z05
It ohould be again pointed out that mixtures of the
dyootuffo of the present invention ~ometimes offer advantages,
e. g. they give a better dye yield than the individual
dyestuff~,
EXAMPLE 1
Stirrod into 2000 g water is 1.0 of the finely
disporMed dy-stuff of the formula
OaN- ~ -N=N_ ~ )-N=N- ~ >-N
3 C2H5
It i9 st~ndardlzod with acetic acid to a pH value of 5-6 and
mixed with 4.0 g ammonium ~ulfate and 2.0 g of a commercial
naphthalono eulfonic acid-formaldehyde condensate dispersing
agent.
Into the dye liquor thus obtained are introduced -
100 g of a polyethylene terophthalate fabric, and it is dyed
1 hour at 130C. ~hon after washing, reductive post_treatment
with a 0.2 ~ alkallno sodlum dithionite solution for 15
minutes at 70_80C~ another wa~hing and finally a drying,
there i8 obtainod ~ doep blue dyed product with very good
color proportios~ particularly a verY good fastness to light
and to hoat. Usin~ polybutylene-torephthalate fabric instead
of polyethylone t~rophthalato fabric, there i9 obtained a
dyeing haYing ~imilar shados and fastne~s properties.
The dyostuff employed in thi~ example was
prepared as follo~t
30,2 B Of 2,5-dimethoxy-4-amino-4'-nitro~ -
azobenzeno are diazotized in 150 g acetic acid with 34,2 g of
41.3 ~ nitro~yl sulfuric acid with external cooling to l15C,
and introducod into a ~olution of 19.6 g 3-N,N-diethylamino-
toluene in 400 g water and
1055Z05
27.6 g technical hydrochloric acid (D = 1,15). The reaction
temperature i9 maintained during the coupling at 0 to +5C
by the addition of ca. 500 g ice. After a one-hour stirring
a solutlon of 136 g sodium acetate in 250 g water i9 run in
for the completion of the coupling. The resulting dyestuff is
filtered off upon completion of the coupling, washed with
water and dried, It is suitably purified by recrystallization
from n-butanol and is a blackish pow~er which di~601ves to a
blue color in concentrated ~ulfuric acid.
EXAMPLE 2
A polyethylene terephthalate fabric is padded at
30C on a pad with a liquor which contain~ 30.0 g of the
finely divided dyestuff of the formula
3 1 ~ 3 12 5
02N- ~ -N=N- ~ -N=N- </ ~ -N
3 C2H5
1.0 g polyacrylamide having a K value of 120, 0.5 g of a
polyglycol ether of oleyl alcohol having sixteen ethylene
oxide moieties per mol, and 968.5 g water. The fabric i8 then
dried and fixed for 60 ~econds at 210 C in a thermofixing
frame. After a ~ubsequent washing and finishing, as
described in Example 1, there is obtained a blue dyeing
having very good fastnes~ properties.
The dyestuff i~ prepared in ac(~ordance wi~h the
data in Example 1 by the use of 21.5 g 3-N,N-diethylamino-
anisole in the coupling, It is suitably l)urified by
recrystallization from n-butanol and is a blackish powder
which dissolves to a blue color iJI concentrated sulfuric
acid.
lOSS205
I'
'' i
EXAMPLE 3
30.0 g of the dyestuff of the formula
o2~3N-~ N=U~N
are incorporated in a fine division into a printing paste which
contains 45.0 g c~rob bean flour, 6.0 g 3-nitrobenzene sulfoniç
acid sodium, and 3.0 g citric acid per 1000 g. After printing
with this paste, then drying and fixing in the thermofixLng frame
for 45 seconds at 215C, washing and finishing, as described in
Example 1, there is obtained on a polyester fabric a deep blue- ~
gray print having very good color p~operties, particularly a very 3
good fastness to light and heat. ?
The dyestuff employed may be prepared in accordance with
the data in Example 1 by the use of 17.9 g N,~-diethylaniline in , ~
the coupling. It is suitably purified by recrystallization from ~ ¦
n-butanol, and is a blackish powder which dissolves to a reddi8h- '
brown color in co~centrated sulfuric acid. I ~¦
EXAMPLE 4
1.0 g of the finely dispe~rsed dyestu~f of the ormula
Cl ~3C0
02N- ~ -N=N- ~ -N=~
.
16.
1055205
is stirred into 2000 g water. It is standardized with acetic
acid to a pH value of 5-6 and mixed with 4.0 g ammonium sulfate
and 2.0 g of a commercial naphthalene sulfonic acid formaldehyde
condensate dispersing agent. Into the dye liquor thus obtained
100 g of a poly~thylene terephthalate fabric are introduced and
dyed 1 hour at 130C.
After a subsequent washing, reductive post-treatment
with an 0.2% alkaline sodium dithionite solution for 15 minutes
at 70-80C, another washing and finally a drying, there is ob-
tained a blue-violet dyeing with very good color properties,
particularly a very good fastness to light and heat.
The dyestuff used in this example is prepared as
follows:
37.0 g 2,5-dimethoxy-4-amino-2',6'-dichloro-4'-nitro-1,1'-azo-
benzene are diazotized at 15C in 150 g acetic acid with 34.2 g
of 41.3% nitrosyl 8ulfuric acid with external cooling, and intro-
duced into a solution of 19.6 g 3-N,N-diethylaminotoluene in
400 g water and 27.6 g technical hydrochloric acid (D = 1.15).
The reaction temperature during the coupling is malntained at 0
to 5C by the addition of ca. 500 g ice. After a one-hour
stirring a solution of 136 g sodium acetate in 250 g water is
allowed to run in. The resulting dyestuff is filtered off upon
completion of the coupling, washed with water and dried. It is
suitably purified by recrystallization from n-butanol and is a ~ !
blackish powder which dissolves to a blue-violet color in con-
centrated sulfuric acid.
.
,
17.
1055Z05
EXAMPLE 5
A iabric of polyethylene terephthalate is padded at
30C on the pad with a liquor which contains 30.0 g oi the ii-
nely divided dyestufi oi the iormula
Cl H3CO OCH
02N ~ N-N ~ N=N ~ N
Cl H3CO
1.0 g oi polyacrylamide having a K value oi 120, 0.5 g oi a po-
lyglycol ether oi oleyl alcohol having twenty ethylene oxide
moieties per mol, and 968.5 g water. The iabric is then dried
and iixed ior 60 seconds at 210C in a thermoiixing ~~ame.
Aiter a subsequent washing and iinishing as described in
Example 1, there ls obtained a blue-gray dyeing having very
good iastness properties,
The dyestuii is prepared in accordance with the data
o~ Example 4 by the use oi 21.5 g 3-N,N~diethylaminoanisole in
the coupling. It is suitably puriiied by recrystallization irom
n-butanol, and is a blackish powder which dissolves to a blue-
violet color in concentrated suliuric acid.
EXAMPLE 6
30.0 g oi the dyestuii oi the formula
02N~N=N~N=N~)--N
1 H3CO
are incorporated in a iine division into a printing paste which
contains 45.0 g carob bean ilour, 6.0 g 3-nitrobenzene sul~onic
acid sodium, and 3.0 g citric acid per 1000 g. Aiter printing,
18
1055Z05
drying and fixing in the thermofixing frame for 45 seconds at
215C, washing and finishing as described in Example 1, there
is obtained with this printing paste on a polyester fa~ric a
deep blue-gray print having very good color properties, particu-
larly a very good fastness to light and heat.
The dyestuff employed may be prepared in accordance
with the data in Example 4 by the use of 17.9 g N,~-diethylani-
line in the coupling. It is suitably purified by recrystalliza-
tion from n-butanol and is a blackish powder which di~solves to
a blue-violet color in concentrated sulfuric acid. I
EXAMPLE 7
' ;" .
100 g polyester material are treated for 30 minutes at
121C in 1500 g ethylene tetrachloride in which 2.0g of the dye-
stuff described in Example 3 had been dissolved. The dyed fabric .'
is washed with warm and cold ethylene tetrachloride, and a full ¦
blue-gray dyeing having very good color properties is obtained.
EXAMPLE 8 1 ¦
~ ,~ .
The procedure of Example 7 is repeated but the dyestuff
used is 2.0 g of ,he dyestuff described in Example 6. There is
obtained an e~ually full b~ue-gray dyeing having very good color
properties.
The following table indicates further dyestuffs usable
according to the invention, which on polyester materials yield
equally deep blue to gray dyeings or prints with equally good t
color properties. This table lists species under the generic
formula.
1 9 .
1055205
T A B L R
ORR2 R3
Y R ~ ~ I
X Y Rl R2R3 R4
~ -H -CH3 -H-CH3 -C~3
2. -H -H -CH3 -H-CH3 C2E5
3. -H -H -CH3 -H3 7( ) 3 7( ~
4. -H -H -CE3 -HC2H5 3 7( )
5. -H -H -CH3 -HC2H5 3 7(
6. -E -H CH3 -H -CH2-CH=CH2 -CH2-CH=CE2
7. -H -H -CH3 -HC2H5 -CH2-CH=CH2
8. -H -H -CH3 -H-C4Hg(n) -C4Hg(n)
9. -H -H -CH3 -HC2H5 -C4Hg(iso)
10. -H -H -CH3 -HC2H5 -C4Hg(tertr)
CH3
11. -H -H -CH3 -H-CH3 CH2 11
CH2
12. -H -H -CH3~ -H-CH3 -CH2-CH=CH-CH3
13. -H -H C2H5 -HC2H5 C2H5
14, -H -H -CH=CH2 -~3 7( ) 3 7( )
20.
1~355~05
X Y Rl R2 R3 R4
15. -H -H -C4Hg(n) -H -CH3 -CH3
16. -H -H -CH3 -Cl -CH3 -CH3
17. -H -H -CH3 -Cl C2H5 C2H5
18. -H -H -CH3 -CH3 -CH3 -CH3
19. -H -H C2H5 -CH3-CH3 -CH3
20. -H -H -CH3 -CH3-C~3 C2~5
21. -H -H -C~3 -CH33 7( ) 3 7( )
22. -H -H -CH3 -CH3C2H5 3 7(
23. -H -H -CH3 -CH3C2H5 -CH2-CH=CH2
24. -H -H -CH3 -CH3 _C4Hg(n) _C4Hg(n)
25. -H -H -CH3 -CH3 -C~3 -C4Hg(iSo)
26. -H -H3 7( ) -CH3 C2H5 C2 5
27. -H -H-C3H? (iso) -CH3 C2H5 C2~5
28. -H -H -CH3 2 5 3 -CH3
29. -H -H -CH3 2 5 2 5 C2H5
30. -H -H C2H5 -C4Hg(n~ C H C2H5
31. -H -H -CH3 3 3 -CH2-CH3
21.
l~S5205
X Y Rl R2 R3 R/l
32. -H -H -CH3 -OCH2-CH=CE2 -C2H5 C2~5
fH3
33. -H -H C2H5 -Cl C2H5 -CH2-C
CH2
34. -H -H -CH3 -OCH3 -CH3 -CH3
35. -H -H -CH3 -OCH3 -CH3 C2H5
36. -H -H -CH3 C2H5 C2H5 C2H5
37. -H -H C2H5 C2H5 C2H5 C2H5
38. -H -H -CH3 -OC3H7(iso) -CH3 -CH3
39. -H -H -CH3 -OC4Hg(n) C2H5 C2H5
40. -H -H -C4Hg(sec-) -OCH3 -CH3 -CH3
41. -H -H -CH3 -OCH3 C2H5 -CH2-CH=CH2
42. -H -H -c~3 -OCH3 C2H5 4 9(
43. -H -H -c~3 -O-CH2-CH=CH2 -C2H5 2 5
44. -H -H C2H5 _O-CH2-CH=CH2 -CH3 -CH3
22.
1~55;~05
X Y Rl R2 R3 R4
45. -Br -Br -CH3 -H -CH3 -CH3
46. -Br -Br -c~3 -H -CH3 C2H5
47. -Cl -H -CH3 -H3 7( ) 3 7( )
48. -Cl -Br -c~3 -HC2H5 3 7( )
49. -Cl -Br -CH3 -HC2H5 3 7(
50. -51 -H 3 _c~2-C~=C~2 -C~2-CH=CH2
5i. -Cl -H -c~3 -HC2H5 -CH2-CH-CH2
52. -Cl -Cl -CH3 -H-C4H9(n) -C4~9(n)
53. -Cl -Br -c~3 -HC2H5 -C4Hg(i80)
54. -Cl -Br 3 -C2~5 -C4Hg(t8rt.)
CH3
55. -Cl -H -CH3 -H -CH3 -CH2-1
56. -Cl -H -CH3 -H -CH3 -CH2-C~sCH_CH3
57. -Cl -Cl -C2~5 -H -C2E5 -C2H5
23,
1~55205
X Y Rl R2 R3 R4
58. -Cl -Cl -CH~CH -H -C3H7(n) -C3H7(n)
59. -Cl -H -C4Hg(n) -H -CH3 -CH3
60. -Cl -Cl -CH3 -Cl -CH3 -CH3
61. -Cl -H -CH3 -Cl C2H5 C2H5
62. -Br -Br -CH3 CH3 CH3 -CH3
63. -Cl -BrC2H5 CH3 CH3 -CH3
64. -Cl -H -CH3 CH3 CH3 C2H5
65. -Cl -Cl-CH3 -C~3 -c3H7(n)i -C3H7(n)
66. -Cl -Br-CH3 -CH3 -C2H5 C3H7(iso)
67. -Cl -Br-CH3 -CH3 -C2H5 -CH2-CH-CH2
68. -Cl -H -CH3 -CH3 -C4Hg(n) -C4H9(n)
69. -Cl -H -CH3 CH3 CH3 -C4H9(iso)
70. -Cl -ClC3H7(n) -CH3 -C2H5 C2H5
71. -Cl -Cl-C3H7(iSo) -CH3 C2H5 -C2H5
24
1055205
X Y Rl R2 R3 R4
72.-Br -Br -CH3 C2H5 -CH3 -CH3
73.-Cl -Cl -CH3 C2H5 C2H5 -C2H5
74.-Cl -H C2H5 -C4H9(n)-C2H5 C2~5
75. -Cl -Br -CH~ -OCH3 -CH3 -CH2-C~3
76. -Cl -Cl -CH3 _0CH2-CH~CH2 -C2H5 C2H5
Cj~3
77. -Cl -Cl C2H5 -Cl -C2~5-CH2-C
C~2
780 -Cl -Cl -CH3 -OCH3 -CH3 -CH3
79. -Cl -Br -CH3 -OCH3 -CH3 C2H5
80. -Cl -Cl -CH3 C2H5 -C2H5-C2H5
81. -Br -Br C2~5 C2H5 -C2H5C2H5
82. -Cl -Br -CH3 OC3H7(iso) -CH3 -CH3
83. -Cl -Cl -CH3 -oC4H9(n) -C2H5-C2H5
84. -Cl -Cl -C4H9(secO) -OCH3 -CH3 -CH3
1055205
X Y Rl R2 R3 R4
85. -Cl -H -CH3 -OCH3 C2H5 -CH2-CH=CH2
86. -Cl -Br -CH3 -OCH3 C2H5 -C4H9(i~o)
87. -Cl -Cl -CH3 _-CH2~cH CH2 C2H5 C2H5
88. -Br -Br -C2H5 -O-CH2-CH'cH2 -C~3 -CH3
89. -Cl -H -CH3 -H C2~5 C2H5
go. -Cl -H -CH3 -C~3 C2H5 C2~5
91. -Cl -H -CH3 -OCH3 C2H5 C2H5
92. -Cl -Br CH3 _~ C2H5 C2H5
93. -Cl -Br -CH3 -CH3 C2H5 C2H5
94. -Cl -Br -CH3 -OCH3 C2~5 C2H5
9S. -Br -Br CH3 ~ C2H5 C2H5
96. -Br -Br -CH3 -CH3 C2~5 C2H5
g7. -Br -Br -CH3 -OCH3 C2~5 C2H5
26.
1055205
X Y Rl R2 R3 R4
98. -CN -H -CH3 -H C2~5 C2H5
99. -CN -H -CH3 -C~3 C2~5 C2~5
100. -CN -EI CH3 OC~3 C2H5 C2H5
101. -CN -H -CH3 -H C2H5 -CH2-CH-CH2
102 .-CN -EI CH3 H C4H9 ( n) C4H9 (n )
103 .-CN -H C 2H5 -CH3 C 3H7 ( n ) C 3~7 ( ~ )
104 . -CN -H -CEI=CH2 -H -C~3 -CH3
105. -CN -Cl CH3 ~~ C2H5 C2H5
106. -CN -Cl -CH3 -CH3 C2H5 C2~5
107. -CN -Cl -CH3 -OCEI3 C2H5 C2H5
108. -CN -Br -CH3 -H C2H5. C2H5
109. -CN -Br -C2H5 -H C2H5 -C2H5
1055Z05
X Y Rl R2 R3 R4
110. -N02 -H -C~3 -H C2H5 C2~5
111. -N02 -H -CH3 -CH3 C2~5 -C2H5
112 . -N02 -H -CH3 -UCH3-C2H5 -C2H5
113 . -N02-EI -CH3 -H --CH2-C~CH2 -CH2-CH~CH2
114 . -N02-EI -C2H5 ~~ -C~3 -CH3
115. -N02 -H -CH3 -Cl C2H5 -C2~5
116. -N02-E~ CH3 ~ -C2H5 ~c4~(tert.
117 . -N02-EI -CH3 -H -C2~5 -CH2-CEI~CH3
118. -N02-Cl CH3 EI C2H5 C2H5
119 . -N02-Cl ~C~3 -O~H` 3 C2~5 -C2~5
120. -N02-Br CH3 ~ C2H5 C2H5
121. -N02-Br -CH3 -CH3 C 2H5 -C 2H5
28
1055205
SUPPLEMENTARY DISCLOSURE
EXAMPLE 122
a) A mixed dye consisting oi
33 1/3% by weight
OCH3
02N ~ N~N ~ N~N ~ N 3 ~ (IX)
OCH3
33 1/3 % by weight
IOCH3
02N~N-N~N~N~ ~ CH2-CH3
'I=' CH2-CH3
OCH3
33 1/3 ~ by weight
OC~ CH
02N ~ N-N ~ N-N ~ N-~ 3 (XI)
OCH3
can be made in the iol lowing manner:
Into a suspen~ion oi 6000.0 g. water, 1500.0 g. ice, 42.4 g.
N.N-dimethyl-aniline, 52.4 g. N.N-diethylaniline and 47.3 g.
3-N.N-dimethylaminotoluene there are introduced, at O to ~5C.
417.7 g. oi the zinC chloride-double ~alt oi diazotized
4-amino-3. 6-dimethoxy-4~-nitroazobenzene oi the iormula
I CH3 (~)
02N ~ N~N ~ N~N 1/2 Zn~12
With external cooling over one hour.
29
lO55Z05
A~ter three hours the diazo reaction has become
negative. Stirring is done overnight at a temperature
rising up to room temperature. Thereupon the coupling
mixture is heated ior one hour to 90-95& . The resulting
dyestu~f is iiltered with suction, washed out with water
of 80 & . and dried. It is a blackish powder which dissolves
to a blue color in concentrated suliuric acid.
b) 20.0 g. of the mixed dye so obtained are ground with 18.0 g.
ligninsul~onate, whilst adding water, to give a paste
containing 20.0 X dyestufi.
2.0 g. o~ this dyestuii dispersion are stirred
into 2000 g. water. It is standardized with acetic acid to a
pH-value oi S and admixed with 4.0 g. ammonium suliate and
2.0 g. oi a commercial naphthalene sulionic acid-~ormaldehyde
condensate dispersing agent. Into the dye liquor thus
obtained 100 g. oi a polyester iabric based on polyethylene-
glycolterephthalate are introduced and dyed one hour at
130C.
A~ter subsequent rinsing, reductive aiter-
treatment with an 0.2 % alkaline sodium dithionite solution for
15 minutes at 70 to 80& ., another rinsing and iinally
drying, a deep grey-blue dyeing with very good coloristic
properties is obtained.
Compared to the individual components IX, X and XI
(100~) the mixed dye used in this working example distin-
guishes itself by a di~tinctly higher coloring power (125%).
A 20.0 ~ strength dyestu~ paste containing this
dye composition may also be prepared by grinding the
individual components IX, X and XI in water with a dispersant
in the mixture ratio as speci~ied.
~55205
EXAMPLE 123
a) A mixed dye consisting o~
33 1/3 ~ by weight oi the dye oi iormula IX
33 1/3 % by weight oi the dye oi iormula X and
33 1/3 % by weight oi the dye oi iormula XII
l H3
02N ~ N~N ~ N~N ~ `CH2-CH3 (XII)
OCH3
is obtained if the coupling component oi the dye VII as
employed in working example 122a is replaced by 52.4 g.
N-methyl-N-ethyl-aniline.
b) Ii the mixed dye iq submitted to the procedure oi Example
122b it yields slmilar coloristic qualities, in particular
with regard to color tone, iastness propertles and coloring
power (120 %), as compared with the individual components
IX, X and XII.
c) 30.0 g. oi the mixed dye are incorporated in a iine
divlsion into a printing paste which contains 45.0 g.
carob bean ilour, 6.0 g. 3-nitrobenzene sulionic acid
sodium and 3.0 g. citric acid per 1000 grams.
Aiter printing, drying and iixing in the thermoiixing frame
ior 45 seconds at 215C., rinsing and iinishing as described
in Example 122b, para 3 thereoi, there is obtained with
this printing paste on polyester iabric a deep, gray-blue
print having very good coloristic properties and having
a little more red-tinged color tone than the dyeing obtained
with the mixed dye according to Example 122b.
31
lQ55Z05
EXAMPLE 124
a) A mixed dye consisting oi 50 % by weight oi the dyestuii
oi iormula IX and 50 % by weight oi that oi iormula XI i5
obtained ii in Example 122a there are used as coupling
components 63.5 g. N.N-dimethyl-aniline and 70.9 g. 3-N.N-
dimethylamino-toluene.
b) Ii this mixed dye is submitt~d to the procedure oi
Example 122b it yields similar coloristic qualities, in
particular with respect to color tone, fastness properties
and coloring power ~115 %), as compared with the individual
components.
c) A polyethyleneglycolterephthalate iabric is padded on the
padding machine at 30 & . with a liquor (50 ~ squeezing eiiect)
containing 30.0 g. oi the iinely divided mixed dye, 1.0 g.
polyacrylamidé having a K-value oi 120 and 0.5 g. oi a
polyglycolether of the oleyl alcohol-and 968.5 g. water.
Aiter drying, the material is iixed in the thermo-iixing
irame ior 60 seconds at 215C. Aiter subsequent rinqing
and iinishing, a deep, gray-blue dyeing having very good
coloristic properties iq obtained, a~ depicted in Example
122b, para 3 thereoi.
The iollowing Table enumerates iurther mixed dyes
oi the general iormula I which are prepared according to the
procedure given in Example 122a and yield, when applied on
polyester material, blue to gray-blue dyeings.
32
l~SSZOS
No.Rl R2 R3 Mixture ratio
_
125-~ -C~3 -CH3 75
OCH3 CH3 -CH3 25
126 -H -CH3 -CH3 50
-H -CH3 -C~2-CH3 50
127 -H -CH3 -CH2-CH3 25
-CH3 -CH2-CH3 -C~2-CH3 75
128 -H -CH3 -CH3 40
-H -CH2-C~3 -CH2-CH3 10
-C~3 -C~3 -CH3 50
129 -H -CH3 -CH3 20
-C~3 -CH3 -CH3 50
-OCH3 -CH2-CH3 -CH2-CH3 30
130 -H -CH3 -CH3 45
-CH3 -CH3 -CH3 10
-OCH3 -CH3 -CH3 45
131-H -CH3 -CH3 40
-CH3 -C~3 -CH3 25
-OCH3 -CH3 -CH3 25
-OCH3 -CH2-C~3 -CH2-CH3 10
132 -H -c~3 -CH3 35
-H -CH3 -CH2-~H3 25
-H -CH2-C~3 -CH2-CH3 35
_~ -CH2-CH2-CH2-cH3 -CH2-C~2 C 2 3
