Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
5~
The invention provides useful novel disazo pigments of the
formula
~m n 1 Xm ~nzp_
~ V
N ~ OR ~
CH3COCHCONH ~ _ ~ NHOCCHOCCH3 C 3
OR
wherein
~ represents a hydrogen or halogen atom,
Y represents a Cl-C6-alkyl or Cl-C6-alkoxy group,
Z represents a C2-C6-alkoxycarbonyl group,
m is an integer from 1 to 5,
n is an integer from 1 to 4,
p is an integer from 1 to 3, while the sum of m + n ~ p is 5,
Q represents an oxygen or sulphur atom,
V represents a hydrogen or halogen atom, and
. ~ - 2 ~
. ., - .
- .
R represents a Cl-C4-alkyl group.
Particularly intcresting disazo pigments are those of the formula
~lzl X~zl
O P
(~>
N OR N
1 3 ~ I CF3
CH3COCHCONH ~ ~ NHCOCHCOCH3
OR
~herein R has the indicated meaning, Xl and Yl represent hydrogen or
chlorine atoms or methyl groups and Zl represents a hydrogen or chlorine
atom, a methyl group or a Cl-C~-alkoxy group.
The pigments of the present invention are obtained by coupling
the diazo compound of an amine of the formula
B
,
`.
. ~.. ....
5~
m ~ ~ n - l
~ v
H2N ~<~
with a bis-acetoacetylphenylenediamine of the formula
0
C~3COCI'12COi~}I~lOC5}120CC~
OR
in the molar ratio 2:1.
The diazo component is in particular one of the formula
Xl~l
H2N ~ `
~F3
wherein Xl, Yl and Zl have the indica~ed meanings.
The following known diazo components may be cited by
way of exampLe:
- .
- : . . .,,;, . ,. .. ~
. ~-. . ~
2-amino-4-trifluoromethyl-diphenyl ether
2-amino-2'-chloro-4-~rifluorornethyl-diphenyl ether.
2-amino-3'-chloro-4-trifluoromethyl-diphenyl ether
2-amino-4'-chloro-4-trifluoromethyl diphenyl ether
2-amino-2l~4~-dichloro-4-trifluoromethyl-diphenyl ether
2-amino-2',5'-dichloro-4-trifluoromethyl-diphenyl ether
2-amino-3',4'-dichloro-4-trifluoromethyl-diphenyl ether
2-amino-2',4',S'-trichloro-4-trifl.uoromethyl-diphenyl ether
2-amino~2',4',6'-trichloro-4-trifluoromethyl-diphenyl ether
2-amino-2',3',4',6'-tetrachloro-4-trifluoromethyl-diphenyl ether
2-amino-2',3',4',5',6'-pentachloro-4-trifluoromethyl-diphenyl
ether
2-amino-2'-chloro-6'-methyl-4-trifluoromethyl-diphenyl ether
2-amino-4'-chloro-2'-methyl-4-trifluoromethyl-diphenyl ether
2-amino-4'-chloro-3'-methyl-4-trifluoromethyl-diphenyl ether
2-amino-2'-methyl-4-trifluoromethyl-diphenyl ether
2-amino-3'-methyl-4-trifluoromethyl-diphenyl ether
2-amino-4'-methyl-4-trifluoromethyl-diphenyl eLher
2-amino-3',5'-dimethyl-4-trifluoromethyl-diphenyl ether
2-amino-2',4'-dimethyl-4-trifluoromethyl-diphenyl ether
2-amino-2'-methoxy-4-trifluoromethyl-diphenyl ether
2-amino-3'-methoxy-4-trifluoromethyl-diphenyl et'n~r
2-amino-4'-methoxy-4-trihloromethyl-diphenyl ether
2-amino-4'-carboethoxy-4-trifluoromethyl-diphenyl ether
2-amino-4-trifluoromethyl-diphPnyl ether
2-amino-4'-chloro-4-trifluoromethyl--diphenyl ether
~ ~ ,
, ~
3~
2-amino-5-chloro-4-trifluoromethyl-diphenyl ether
2-amino-2',5-dichloro-4-trifluoromethyl-diphenyl ether
2-amino-4',5-dichloro-4-trifluoromethyl-diphenyl ether
2-amino-2',4',5-trichloro-4-trifluoromethyl-diphenyl ether
2-amino-2',5',5-trichloro-4-trifluoromethyl-diphenyl ether
2-amino-2',4',5',5-tetrachloro-4-trifluoromethyl-diphenyl ether
2-amino-5-chloro-4'-methyl-4-trifluoromethyl-diphenyl ether
2-amino-5-chloro-4'-methoxy-4-trifluoromethyl-diphenyl ether
2-amino-4',5-dichloro-6'-methyl-4-trifluoromethyl-diphenyl ether
The diazo components are obtained by reduction of the
corresponding nitro-trifluoro-diphenyl ethers, which have been prepared
for example from nitro-trifluoromethylbenzenes and phenols, under
alkaline conditions, in dimethyl sulphoxide or dimethyl formamide.
The coupling components, which are also known, are obtained
in simple manner by treating the corresponding known phenylenediamines
with diketene or alkyl acetate. Examples of such phenylenediamines are:
2,5-dimethoxy-1,4-phenylenediamine
2,5-diethoxy-1,4-phenylenediamine
2,5-dipropoxy-1,4-phenylenediamine
2,5-diisopropoxy-1,4-phenylenediamine.
- 6 -
~ ` ' '
The coupling preferably takes place in a weakly
acid medium, advantageously in ~he presence of conventional
agents that promote the coupling. Such agents are in particu-
lar dispersants, for e~ample aralkylsulphonates, such as
dodeeylbenzenesulphonate, or l,l'-dinaphthylmethane-2,2'-
disulphonic aeid or polycondensation products of alkylene
oxides. The dispersion of the eoupling component can also
advantageously eontain proteetive colloids, for example
methyleellulose or minor amounts of inert organie solvents
whieh are sparingly soluble or insoluble in water, for example
optionally halogena~ed or nitrated aromatic hydrocarbons, for
example, benzene, toluene, xylene, chlorobenzene9 dichloro-
benzene or nitrobenzene, and also aliphatic halogenated hydro-
earbons, for example earbon tetrachlorlde or trichloro-
ethylene, as well as organie solvents whieh are miscible with
water, for example, aeetone, ethylene glyeol monomethyl ether~
methyl ethyl ketone,methanol, ethanol or isopropanol.
The eoupling ean also advantageously be carried out
by eontinuously eombining an aeid solution of the diazonium
salt with an alkaline solution of the eoupling eomponent in a
mixing nozzle, whereupon an immediate coupling of the eomponent
oeeurs. Care must be taken that the diazo eomponent and the
coupling eomponent are present in equimolecular amounts in the
mixing nozzle, although a slight excess of coupling component
proves to be advantageous. This is most simply accomplished
by controlling the pH of the liquid in the mixing nozzle.
-- 7 --
. ~ -
. . ~ :
. . , , -
Furthermore, intense ~urbulent mixing of the two solutions
in the miX~ nozzle must be ensured. The resultant colourant
disperion is continuously drawn off from the mixing no~zle
and the colourant separated by filtration.
Finally, the coupling can also be carried out by
suspe~ng the diazo component with the coupling component in the
molar ratio 2:1 in an organic solvent and treating the coup
ling mixture with a diazotising agent, in particular with an
ester of nitrous acid, such as methyl, ethyl, butyl, amyl or
octyl nitrite.
The pigments usually precipitate at elevated temperature
and can be isolated in pure form by filtration and subsequent
removal of any impurities by washing them with an organic
solvent.
The pigments have in general a good texture and can be
widely used as crude products. If necessary or desired, the crude
products can be converted into a finely dipersed form by
grinding or kneading, advantageously using grinding assistants,
such as inorganic and/or organic salts in the presence or ab-
sence of organic solvents. After the grinding procedure, the
assistants are removed in the conventional manner: soluble
inorganic salts for example with water, and water-insoluble
assistants for example by steam distillation.
The properties of the crude pigments can often be
improved by treating them with organic solvents, preferably
those having a boiling point above 100C. Particularly
-- 8 --
., ~ ,
.,
`
::
suitable organic solvents are: benzenes which are substituted
by halogen atoms, alkyl or nitro groups, for example xylene,
chlorobenzene, o-dichloroben~lene or nitroben~ene, as well as
pyridine bases, such as pyridine, picoline or quinoline, and
also ketones, for example, c:yclohex-anone; ethers, for example
ethylene glycol monomethyl and monoethyl ether; amides, such as
dimethyl formamide or N-methylpyrrolidone, as well as sulpho-
xoneor water under pressure.
The aftertreatment is effected preferably by heating the
pigment in the solvent to 100-150C, when in many cases an
increase in the gra~ular size occurs. The fastness to light
and migration of the resultant pigmen~s are thereby favourably
influenced,
The pigments according to the invention are suitable
for colouring organic material of high molecular wPight, for
example cellulose ethers and esters, polyamides and polyure-
thanes or polyesters, acetyl cellulose, nitrocellulose,
natural resins or synthetic resins, such as polymerisation
or condensation resins,for example aminoplasts, in particular
urea and melaminelformaldehyde resins, alkyd resins,
phenolic plastics, polycarbonates, polyolefins, such as
polystyrene, polyvinyl chloride, polyethylene, polypropylene,
polyacrylonitrile, polyacrylates, rubber, casein, silicone
and silicone resins, individually or in mlxtures.
It is immaterial whether the cited materials of high
~ ~ 5~ ~ ~
molecular weight are in the form of plastics, melts or in the
form of spinning solutions, varnishes, paints or printing
inks. Depending on the use to which they are put, it is
advantageous to use the new pigments as toners or in the form
of preparations,
In addition to the p~lre pigment, the preparations can
a~ditionally contain, for example, abietic acid or esters
thereof, ethyl cellulose, cellulose ace~obutyrate, alkaline
earth salts of higher fatty acids, fatty amines~ for example,
stearylamine or rosinamine, vinyl chloride/vinylacetate
copolymers, polyacrylonitrile or polyterpene resins or water-
soluble dyes, for example dyestuff sulphonic acids or the
alkaline earth salts thereof.
The pigments of the present invention are distinguished
by good fastness to light, migration and weather. They also
have good dispersibility, transparency and brilliance,
as well as excellent resistance to alkali and high colour
strength. Compared with US patents 2,591,470 and
3,872,078, they are distinguished by improved lightfastness
and resistance to weathering.
In the following Examples which illustrate the
invention, the parts and percentages are by weight unless
otherwise indicated.
- 10 -
Example 1
25.3 parts of 2-amino-4~trifluoromethyl-diphenyl
ether are stirred in 300 parts by volume of glacial acetic acid
with 25 parts by volume of conc. hydrochlo~ic acid, where-
upon the chlorohydrate of the base is formed. The reaction
mixture is then cooled to -5C by addition of 300 parts of ice
and diazotised by adding 25 parts by volume o 4N sodium
nitrite. The yellow diazo solution is stirred at 0 to 5 C
until only traces of nitrous acid can still be detected. The
diazo solution is then filtered clear by addition of decolouris-
ing carbon. The filtrate is adjusted to pH 4 by addition of
48 parts of sodium acetate. Simultaneously, 16.8 parts of
2,5-dimethoxy-1,4-bis-acetoacetylaminobenzene are dissolved in
800 parts of water with 12 parts by volume of 40 % sodium
hydroxide solution and 5 parts of n-butylsulphoricinoleate
are added. This solution is filtered clear with 0.5 part of
decolourising carbon and then added dropwise, with efficient
stirring, to the diazo solution over the course of 1 to 1 1/2
hours. The temperature of the reaction mixture riseS to 15 to
20 C. When the dropwise addition is complete, no more diazo
compound can be detected in the mixture. The coupling mixture
is stirred for 1 hour at room temperature, then heated to
80-85C and filtered hot. The filter cake is washed ~ree of
salt and dried in vacuo at 95 -100C, aff-ording 40 parts
of a yellow colourant of the formula
,
. .
~F3 ~ C--7F3
C~13COC~ICO`~ N~OCG`IIOCCH~
O C1l13
40 parts of this pigment are stirred in 600 parts by volume
of dimethyl formamide for 8 hours at 145-150 C, whereupon
it assumes a homogeneous crystalline form. Microscopic
examination reveals fine, yellow particles 5-15 ~ in length.
After filtration at 140C, washing with boiling cellosolve
until the filtrate runs clear, expelling the cellosolve with
ethanol and drying, there are obtained 10.2 parts of a brilli-
ant yellowish orange pigment dye. It colours plastics,
such as polyvinyl chloride, in yellowish orange shades of
excellent fastness to migration. The treatment in the organic
solvent can be carried out direct with the moist filter cake
without first drying it. The moist filter cake can be stirred
in picoline at 100-120C, filtered, washed with methanol and
subsequently with dilute hydrochloric acid, or it is stirrred
in chlorobenzene, o-dichlorobenzene or nitrobenzene, and freed
from water by azeotropic distillation and then worked up as
described hereinabove. The pigment colours polyvinyl chloride
- 12 -
, , ., . - - , -
. 1
.- ,:, : . : .
:- : ,: ~ :: :, ..
- -: ~ . .. , . ,
~s~
in yellowish orange shades of excellent fastness to ligh~,
weather and migration.
The corresponding pigments with chlorine atoms instead
of trifluoromethyl groups are disclosed in US patent specifi-
cation 2,591,470, but they have po~rer fastness to light and
weathering in the colouration of PVC and lacquers,
The following Table lists further coloura~ts which are
obtained by coupling the diazotised bases of column I with the
bisacetoacetic arylides of the diamines of column II.
Column III indicates the shade of polyvinyl chloride sheets
coloured with 0.2 % of these pigments.
- 13 -
' '
~ ,
~s~
. Ex. Diazo Component Coupling ~omponent ~ Sha
2 2-amino-4-trifluoro- 2,5-diethoxy-1,4- yellowish
methyldiphenyl ether phenylenediamine orange
. 3 ,l 2,5-dipropoxy-1,4- yellowish
phenylenediamine orange
4 2-amino-2' chloro-4- 2~5-dimethoxy-1,4- yellowish
trifluoromethyl- phenylenediamine orange
diphenyl ether
. 5 ,l 2,5-diethoxy-1,4- yellowish
phenylenediamine orange
. 6 2-amino-4~-chloro-4- 2,5-dimethoxy-1,4- orange
trifluoromethyl- phenylenediamine
diphenyl ether
7 ll 2,5-diethoxy-1,4- orange
phenylenediamine
2,5-diisopropoxy- yellow
1,4-phenylene
diamine
9 2-amino-2',4'-dichlo- 2,5-dimethoxy-1,4- yellowish
ro-4-trifluoro- phenylenediamine orange
methyl-diphenyl ether
10 ll 2,5-diethoxy-1,4- yellowish
phenylenediamine orange
ll 2-amino-2'?4',5'-tri- 2,5-dimethoxy-1,4- orange
chloro-4-trirluoro- phenylenediamine
methyl-diphenyl-ether
12 " . 2,5-diethoxy-1,4- orange
phenylenedi~mine
13 2 amino-3'-methyl-4- 2,5-dimethoxy-1,4- yellowish
trifluoromethyl- phenylenediamine orange
diphenyl ether
]4 ~ . 2,5-diethoxy-1,4- orange ..
phenylenediamine _ _ _
- 14 -
. ~. , : . .
~0~ 8~
~ . . __
Ex. Diazo Component ¦Co~lpling Component Shade in PVC
. .~ . I _ ~ _ I
2-amino-3',5'-di- 2,5-dimethoxy-1,4- orange
methyl-~-trifluoro- phenylenediamine
methyl-diphenyl
ether
l~ ll 2,5-diethoxy-1,4- orange
. phenylenediamine
17 2-amino-2'-methoxy- 2,5-dimethoxy-1,4- orange
4-trifluoromethyl- phenylenediamine
diphenyl ether
18 ,l 2,5-diethoxy-1,4- orange
phenylenediamine
19 2-amino-4'-chloro-2'- 2,5-dimethoxy-1,4- orange
methyl-4-trifluoro- phenylenediamine
methyl-diphenyl
ether
20 ll 2,5-diethoxy-1,4- orange
phenylenediamine
21 2-amino-5-chloro-4- 2,5-dimethoxy-1,4- orange
trifluoromethyl-di- phenylenediamine
phenyl ether
22 ll 2.5-diethoxy-1,4- orange
phenylenediamine
23 2-amino-4',5-dichlo- 2,5-dimethoxy-1,4- yellowish
ro-4-trifluoro- phenylenediamine orange
methyl-diphenyl ether
24, ll 2,5-diethoxy-1,4- orange ..
. phenylenediamine
25 2-amino-2',5'-5-tri- 2,5-dimethoxy-1,4- orange
chloro-4-trifluoro- phenylendiamine
methyl-diphenyl ether
26 It 2,5-diethoxy-1,4- orange
_ phenylenediamine
.. _ .. _ . . .. _
- 15 -
.. . :
p~
Ex.l Diazo Component I Coupling Component Shade ln PVC
27 ¦ 2-amino-2',4',5',5-tetra- 2,5-dimethoxy-1,4- orange
I chloro-4-trifluoromethyl- phenylenediamine
diphenyl ether
2S .. 2,5-diethoxy- 1,4- orange
phenylenediamine
2~ 2-amino-2'-methoxy-5- 2,5-dimethoxy-1,4- orange
chloro-4-trifluoro- phenylenediamine
methyl-diphenyl ether
~ 2,5-diethoxy-1,4- orange
phenylenediamine
31 2-amino-4',5-dichloro-6'- 2,5-dimethoxy-1,4- orange
methyl-4-trifluoro- phenylenediamine
methyl-diphenyl ether
32 ll 2,5-diethoxy-1,4- orange
phenylenediamine
33 2-amino-4'-carboethoxy- 2,5-dimethoxy-1,4- yellowish
4-trifluoromethyl-di- phenylenediamine orange
phenylene ether
¦34 ll 2,5-diethoxy-1,4- yellowish
phenylenediamine orange
135 2-amino-4-trifluoro- 2,5-dimethoxy-1,4- yellowish
methyl-diphenylthio phenylenediamine orange
ethe
l ~ ~
- 16 -
f~
~ .
. .
5~
Example k~
2 g of the pigment obtained in Example 1 are gound
with 36 g of toner dehydrate, 60 g of boiled linseed oil of
medium viscosity and 2 g of cobalt linoleate on a three roll
mill. The yellow prints obtained with the resultant colour
paste are strong and of excellent lightfastnessO
~,~
Example ~
0.6 g of the pigment obtained in Example 1 is mixed
with 67 g of polyvinyl chloride, 33 g of dioctyl phthalate,
2 g of dibutyl tin dilaurate and 2 g of titanium dioxide and
the mixture is processed to a thin sheet for 15 minutes at
160 C on a roll mill. The yellowish orange colouration obtained
is strong and fast to migration, heat and light.
3 ~ ~-}
Example ~
10 g of titanium dioxide and 2 g of the pigment obtained
in Example 1 are ground for 48 hours in a ball mill with 88 g
of a mixture of 26 4 g of coconut alkyd resin, 24 g of
melamin~/orm~1dehyde resin (~0 % solids content),
8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene.
The resultant lacquer is sprayed onto an aluminium sheet, pre-
dried for 30 minutes at room temperature and then stoved for
30 minutes at 120C, giving a brilliant orange finish which
has very good colour strength and is distinguished by very
good fastness to overstripe bleeding, light and weathering.
- 17 -
