Note: Descriptions are shown in the official language in which they were submitted.
1082832
The present invention relates to a process for the dyeing of
high molecular weight organic polymers wherein a pigment which is a perinone
compound of thc gencral formula
r
in which A represents an ortho- or peri-arylene radical selected from the
benzene, naphthalene or anthracene series or a 5- or 6-membered heterocyclic
radical containing 1 or 2 nitrogen atoms, and X represents hydrogen or a
direct bond or a straight or branched alkylene of 1 to 6 carbon atoms, a
vinylene radical or a bridging member of the formula
R
-CO-, -CONH-, -NH-CO-NH-, -CO-N-CO-, -NH-CO-NH-CO-,
-CONH-Y-NHCO-, -NHCO-Y-CONH-
n represents the number 1 or 2 and m = 1 if n = 1, and m = O if n = 2, R re-
presents hydrogen or lower alkyl and Y represents lower alkylene or phenylene,
is incorporated into the polymer melt, spinning solution, lacquer, paint or
printing ink.
-1-
¢~
~ , ~
- : :
1082832
Of particular interest is the use in the process of the
invention of compounds of the formula II
o ~ N ~,,,N ~II)
~ H
C I -la-
:`' '
. ' .
1082f~32
in which A1 represents phenylene radical which is unsubstituted or is sub-
stituted by one or two substituents selected from the group consisting of
fluorine, chlorine, bromine, lower alkyl groups such as methyl, ethyl, or
propy.L groups, lower alkoxy groups such as methoxy, ethoxy or propoxy groups,
hydroxy, phenyl, phenoxy, benzyloxy, lower aIkanoylamino groups such as
acetyl, benzoylamino, lower alkyl-sulfonyl groups, nitro, nitrile, trifluoro-
methyl, carboxy carbalkoxy of 2 to 5 carbon atoms or carboxylic or sulfonic
acid amide which is unsubstituted or substituted at the nitrogen atom by one
or two radicals selected from lower alkyl, phenyl or nitrophenyl, or wherein
A, is a group of formu~La:
o ~ N ~ N
HO ~ OH
wherein A1 is phenylene which is unsubstituted or substituted by 1 or 2 sub-
stituents selected from fluorine, chlorine, bromine, lower alkyl, lower alkoxy,
phenyl, phenoxy, hydroxy, benzyloxy, lower alkanoylamino, benzoylamino, lower
alkylsulfonyl, nitro, nitrile, trifluoromethyl, carboxy, carbaLkoxy of 2 to 5
carbon atoms and carboxylic or sulfonic acid amide which is unsubstituted or
substituted at the nitrogen by 1 or 2 radicals selected from lower alkyl,
phenyl or nitrophenyl; or wherein A1 is a group of the formula
~ , ~ , ~ or
B
. . ..: .
- 1082b~32
~ .'
Of these mention is made of compounds in which A is a group of the
formula
.~ ~9
.
Also of particular interest are compounds of formula III
A
o _~N ~f~N
NO / ~ ON (III~
in which A2 represents a naphthalene or acenaphthene radical, which is unsub-
stituted or is substituted by fluorine, chlorine, or bromine, lower alkyl
such as methyl or ethyl groups, lower alkoxy such as methoxy or ethoxy groups,
hydroxy, phenoxy, nitro, lower aIkanoyl such as acetyl, benzoyl, lower alkanoyl-
amin~ suchdas acetylamino or benzoylamino or carbamoylor sulfamoyl, which are
unsubstituted or are substituted at the nitrogen atom by one or two substituents
selected from lower alkyl and phenyl.
; Further compounds of interest are compounds of the formNla IV
--3--
` ~ ' , . ~-
,
.
1082f~32
~ ,
o ~ =~N ~N
HO / ~ \ OH (IV)
in which B represents a bridge member forming together with the two carbon
atoms to which it is linked a 5- or 6-membered ring, which bridge member con-
sists of carbon and up to two nitrogen ato~s. Preferably the bridge member
consists of two -NH- groups and two groups selected from -CO- and -CS-.
Yet further compounds useful in the invention are those of formula
(V)
~X~
~ ~ O ~ N ~ (V)
NO ~ QN ~O - ~ ~
in which X represents a direct bond, a straight or branched alkylene radical
of 1 to 6 carbon atoms, a vinylene radical or a bridging member of the formula
R
-CO-, -CONH-, -NH-CO-NH-, -CO-N-CO-, -NH-CO-NH-CO-,
-CONH-Y-NHCO-, -NHCO-Y-CONH-
in which Y is lower alkylene or phenylene~ R is hydrogen or lower alkyl and
the phenyl nuclei marked "a" are unsubstituted or are substituted by chlorine,
lower alkyl ~r lower alkoxy.
--4--
B
: .
108Z~32
The dyestuffs may be obtained by reacting 1 or 2 moles of 3,6-di-
hydroxynaphthalic acid anhydride with 1 mole of an aromatic or heterocyclic
ortho- or peri-diamine or tetramine or the salts thereof, optionally in the
presence of acid-binding agents.
The dyestuffs of the formula II may also be obtained by condensing
1 mole of the 3,6-dihydroxynaphthalic acid anhydride with 1 mole of ano-
nitroaniline, then reducing the nitro group to an amino group and effecting
the cyclization to the dyestuff of the formula II.
The aromatic diamines of the benzene, diphenyl, naphthalene, acena-
phthene, anthraquinone, fluorene or phenanthene series, in particular the
ortho-phenylene diamines or ortho- orperi-naphthylene-diamines and the o-nitra-
nilines, used as the starting compounds may contain other substituents, for
example halogen atoms, such as fluorine~ chlorine or bromine atoms, lower
alkyl groups such as methyl, ethyl or propyl groups, hydroxy or lower alkoxy
groups such as methoxy, ethoxy or propoxy groups, aryloxy groups e.g. option-
ally substituted phenoxy groups, aralkoxy groups such as benzyloxy groups,
acylamino groups such as acetyl or benzoylamino groups, alkyl-sulfonyl groups,
nitro, nitrilej trifluoromethyl, carboxylic acid ester groups or carboxylic
acid amide groups and optionally substituted sulfonic acid amide groups.
As tetramines, there may be used 1,2,4,5-tetraminobenzene, in parti-
cular amines of the formula VI
2 ~ X ~ NH2 (VI)
H2N 2
`' ~
~)82~3z
in which X has the meanings given above and the benzene nuclei a may contain
other substituents, for example halogen atoms such as chlorine atoms, lower
alkyl groups or lower alkoxy groups.
The 3,6-dihydroxy-1,8-naphthalic acid anhydride used as the starting
compound may be prepared by sulfonation of 1,8-naphthalic acid anhydride with
about 20-30% oleum at 170 - 200C and by subsequent alkali melt of the 3,6-
disulfonaphthalic acid formed (cf. Chemisches Zentralblatt 1936, II~ 4213-
4214).
The dyestuffs are advantageously prepared in known manner by heating
the components (3,6-dihydroxy- naphthalic acid anhydride and di- or tetraamine)
in water optionally acidified with catalytical amounts of acid or a solvent,
for example acetic acid, ethanol, dimethylformamide or N-methylpyrrolidone.
The reaction is completed after several hours at elevated temperature, pre-
ferably at 80 - 150 C. It may be easily followed by chromatography. In
general, the perinone compounds formed of the formula I precipitate from the
reaction mixture and are isolated by filtration. The addition of water prior
to the isolation may sometimes be of advantage, because some of the compounds
; of the invention show a tendency to delay crystallization.
In some cases, for example with very unstable aromatic di- or tetra-
amines, it may be of advantage to condense, instead of the free base, a mineral
acid salt thereof with 3,6-dihydroxynaphthalic acid anhydride, in which case
the addition of an acid-binding agent, for example alkali metal carbonate or
acetate, warrants a particularly smooth reaction.
In the same manner, a condensation of the 3,6-dihydroxynaphthalic
acid anhydride under comparable reaction conditions with the o-nitroaniline
'
1082~32
from which the unstable diamino compound is derived to the resulting 3,6-
dihydroxynaphthalic acid imide may be of advantage, whereupon a reaction of
the nitro-group standing in ortho-position to the imide-nitrogen, for example
by catalytical or iron reduction is followed and whereupon, in general, the
o-amino-group formed spontaneously closes the imidazole ring under separation
of water. Heating for several hours to elevated temperatures to effect
cyclization has been found necessary only in some cases with kinetically partic-
ularly disadvantageous conditions.
The perinones of formula I have been found to be valuable dyes, in
particular valuable pigments that may be used in finely dispersed form, in-
dividually or as mixtures, for the pigrnentation of high molecular organic
materials, for example for cellulose ethers and cellulose esters, for example
ethyl cellulose, cellulose acetate, cellulose butyrate, for polyamides or
polyurethanes or polyesters, natural or synthetic resins such as those resins
obtained by polymerization, for example aminoplasts, in particular urea-form-
aldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, poly-
carbonates, for polyolefins such as polystyrene, polyvinyl chloride, poly-
ethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, for
rubber, casein, silicone and silicon resins.
The perinones of formula I have already valuable tinctorial properties.
But in many cases, their properties regarding application may often be improved
by an usual pigment finish~ for example by prolonged heating in water and/or
solvents, by distribution by grinding or kneading in the presence of salts,
solvents or dispersants.
The high molecular materials to be dyed may be masses of plastic in
.~
. . -.
108Z832
the form of melts or of spinning solutions, lacquers, paints or printing inks.
The pigments may be used in the form of a pure pigment powder or in
~he form of a dispersion of pigment in a resin. The resins which are suitable
for use as carriers in pigment dispersions are natura] resins, for example
abietic acid or the esters thereof, ethyl cellulose, cellulose acetobutyrate,
alkaline earth metal salts of higher fatty acids~ fatty amines~ for example
stearyl amine or colophonium-amine, vinyl chloride/vinyl-acetate copolymers,
polyacrylonitrile or polyterpene resins or water-soluble resins, for example
resins containi~g sulfonic acid groups or their alkaline earth metal salts.
The next comparable compound of the mono-hydroxy-naphthoylene-
benzimidazole series(known from '~Journal of the Society of Dyers and Colour-
ists", Vol. 85 (1969), page 249) is a typical disperse dyestuff and carnot be
used as pigment because of its insufficient fastness to bleeding and to over-
lacquering.
Thus~ it was surprising and not foreseeable that the introduction
of an additional hydroxy group would result in such considerable modifications
of the properties. In addition to a high tinctorial strength, the pigments
are distinguished
: B
- 1082~32
by an excellent fastness to light, very good purity of colour shade and, in
general, valuable colouristic and utilization properties, in particular by
a surprisingly high fastness to solvents and plastizisers, for example a very
good fastness ~o bleeding, overlacquering, migration and blooming. In view
of these properties and by reason of their easy accessibility, these com-
pounds represent a considerable technical advance.
The following Examples illustrate the invention, parts are by weight.
EXAMPLE 1:
A mixture of 2700 parts of glacial acetic acid, 130 parts of 3,6-dihy-
droxynaphthalic acid anhydride and 67.3 parts of o-phenylene-diamine was
heated, while stirringJ for 5 - 6 hours, to the boiling temperature
~ ~ 115 - 120 C). The reaction mixture was allowed to cool, the dyestuff
of the formula
>~
Q N N
H0 ~ OH
that had precipitated was filtered off with suction, washed with water until
neutrality and dried at 80 C. 165 Parts (= 97% of the theory) of a yellow
pigment were obtained; the pigment was found to be excellently suitable for
the dyeing of synthetics and plastic masses and yielded dyeings with
excellent fastness properties.
Better fastness properties, in particular very good fastness to bleeding
and overlacquering, were obtained when stirring the water-wet pigment before
drying for 5 hours with the 5-fold amount of dimethylformamide at 100 - 110 C,
. ~-.,. ,, ; , - -
iO8Z~3Z
filtering it off while hot, washing it with water and drying it.
If, instead of glacial acetic acid, the same quantities of formic
acicl were used, the pigment was formed with comparable yields and showed the
same fastness properties.
~X~MPLe 2:
23 Parts o 3,6-dihydroxynaphthalic acid anhydride, 17.4 parts of
1,8-naphthylene-diamine and S parts of propionic acid were stirred consecu-
tively into 250 parts of water and the mixture so obtained was heated for 8
hours in an autoclave to 130 - 140 C, whereupon a pressure of 3 - 4 atmos-
pheres rose up. The mixture was then cooled, the pressure was released and
- the compound formed of the formula
;; ~ .
~IO ~ OH
was filtered off with suction, washed with water and dried at 100 C. 35
Parts (= 99% of the theory) of a red pigment were obtained, which pigment was
found to be excellently suitable for the preparation of printing inks, lac-
quers and paints and permits, in these fields of application, dyeings with
high colour intensity and excellent properties of fastness.
When the 1,8-naphthylene-diamine was replaced by a corresponding
amount of 4-methoxy-1,8-naphthylene-diamine, there was obtained a somewhat
more bluish pigment having comparable properties of fastness and higher
tinctorial strength.
-::.
- 1 0 -
.
,
Z~32
F:XA~JPLE 3:
23 Parts of 3,6-dihydroxynaphthalic acid anIIydride, 25,3
parts of 2,4-diaminoanisole-dicIIlorohydrate, 400 parts of iso-
propanol and 20.5 par~s of sodium acetate were heat~ in an
autoclave for 10 hours to 140 _ 145 C. After coolin~, the
pressurc was rcleased and the dyestuf f obtained was filtered
off with suction. Af~er washing with isopropanol and water,
the dyestuff was dried at 80 C.
31 Parts (= 93.4 % of the theory) of an orange yellow
pigment were obtained which was found to be suita~le for the
preparation of light and weather fast lacquers as well as for
the colouring of plastizised polyvinyl chloride. Subsequent
heating for 5 hours of the water-wet filter cake with the
10-fold amound of a mixture of 9 parts of water and 1 part
of isobutanol to 150 C yielded a pigment which had increased
covering power and improved fastness to li~ht and to weather.
~ XA~IPLE 4:
23 Parts of 3,6-dihydroxynaphthalic acid anhydride and
18 parts of 3-nitro-4- aminobenzonitrile were introduced into
400 parts of 95% acetic acid and the mixture was then heated
to 90 C. After 2 lIours~ the nitroimide of the formula
CN
~2
0~0
~ ~ ~ ~ ~ OH
separated. Then, 14 parts of iron po~rrder we-re added portionwise
1~)82832
within 2 nours. The reaction was exothermic and took place
at 100 C. The wll~le was heated for 3 hours to 100 - 105 C,
dliluted with 600 parts of water and filtered with suction while
hlot, The filter cake which was still contaminated with basic
iron ~c~tate was then introduced into 1000 parts o~ dimethyl~
formamide and heated to the boilin~ temperature. After addition
of 5 parts of active carbon, the mixture was filtered with
suction through a clarifying filter, the filtrate was cooled
to 50 C while stirring and the compound of the formula
CN
~ .
O ~ '~
}10 ~~ C'i
whlch had precipitated was filtexed off, ~ashed with water
and dried,
30 Parts of a greenish-yellow pigment (= 91.7% of the theory)
were obtained; the pigment was found to have an
excellent fastness to light and to be excellently suitable for
: the preparation of lacquers, in particular lacquers with
` metallic effect.
The reduction of the intermediarily formed nitroimide may
be effected with the sams result catalytically with hydrogen,
which also induces spontaneous cyclization to th~ compound of
the invention.
:: For this purpose, the o-nitroimide isolated ~y filtration
.vas heated in 1500 parts of dimethylformamide with addi.tion of
1 part of a nickel catalyst and under a hydrogen pressure of 50
atmospheres gau~e to 130 C~, until no absorption of gas ~as
10~2~32
stated. The pressure was released, the mixture was filtered while hot to
remove the catalyst and the filtrate was cooled, while stirring, to 50 C,
whcroupon the pigment separated. Its isolation was effected as described
abovo.
EXAMPLES 5 ~
When replacing in Example 4 the 3-nitro-4-amino-benzo-nitrile by
aliquot amounts of other o-nitranilines and working in the manner described,
there were obtained other pigments of the invention corresponding to the
general formula
' ~ .
O N N
110 ~ 0}~
with the yields and shades indicated in table l.
T a b l e
Example X Yield Shade
Cl 96.3 % greenish yellow
6 -OC2H5 97.5 % orange
7 -NHCOCH3 98.5 % orange red
8 CH3 94.8 % yellow
9 Br 98.l % greenish yellow
2 3 96.5 % greenish yellow
ll OH 93.0 % reddish yellow
- 13 -
:
~08283Z
ExAr.lPLE 12:
23 Parts of 3,6-dihydroxynaphthallc acid anhydride, 18.3
parts o~ 3,4-diaminobenzoic acid and lS0 parts o~ N-methylpyrro-
lidone were stirred, 5 parts of formic acid were added and the
mlxture was heated for 5 hours to 120 - 130 C. The precipitate .
of the compound oi the ~ormula
~,OO
.'
~10 ~ Ojl
formed was completed by the addition of 200 parts of water, the
ocompound was filtered off with suction, washed witll water and
dried.
33.8 Parts (97,7 % of the theory) of a greenish-yellow
pigm::nt were obtained; after grinding with a salt, in particular
with the 5-fold amount of sodium sul~ate, this pigment was found
to be particularly suitable for the preparation of transparent
lacquers.
- The following Tables 2 to 5 show other compounds of the
~ormulae II to V of the invention which had been prepared according
to one o~ the processes of the invention, in particular in a
manner analogous to that described in the foregoing Examples,
and indicate also the corresponding yields and shades,
_ 14 -
. _ .
,.. ' ~ ~
108Z~32
T a b 1 e 2
(Dyestuffs of the formula II)
Examplo A1 Yield Shade
cll3
1.; ~ 96.8 % Yellow
~H3
14 ~ ~ 94.8 % yellow
)~ ,
F
~ greenish
~ 91.9 % yellow
CH3
: CH3-CH
16 ~ 89.5 % yellow
:` .
- .,
.
1082~32
Example Al Yield Shade
Cl Cl
17 ~ 98.5 % greenish yellow
18 ll7C30 ~ 92.8 % yellow
19 ~ 97.0 % orange
~ .
~ 98.3 % reddish yellow
. ~I
N2 ~
21 ~ 98.6 % greenish yellow
22 NHCO ~ 98.0 % orange
~ .,.
>=<
CN
23 ~ 94.8 % greenish yellow
24 ~ 9l.9 % g~eenish yellow
.~ - 16 -
1082~32
E.~an~ple Al Yield Shade
_ . _
COOC4~l9
2S ~ 89.8 % greenish yellow
CON1 12
26 ~ 99.0 % greenish yellow.
,N 2
27 97.8 % greenish yellow
- CONH
~, C 2H5
28 . S02N 96.9 % greenish yellow
2~1S'
)~< '
~: 29 ~ 94.5 % yellow
~ 92.8 % rellow
31 o = ~ o 93.7 % red orenge
- 17 -
D
`
` -. ~ , .
~. ` .-.
- ~ . .
, . .
1082~32
Example Al Yield Shade
/~
32 ~ -o 93.0 % y~llow
~,
33 ~ 94.5 % yellow
34 ~ ~ 94.~ % yellow
T a b l e 3
Example A2 Yield Shade
.
~ 35 ~ 96.8 % bluish red
:~ CH2- CH2
36 ~ 95.5 % red
- 18 -
. ' .
'
:
10~2832
Example A2 Yield Shade
502N~ ~ 99.1 ~ bluish red
OC2"5
38 ~ 95.8 ~ red
T a b l e 4
(Dyestuffs of the formula IV)
Example B Yield Shade
N,H ~'
39 5 ~ H 95.0 ~ yel10w
NH~
0 ~ NH 94.9 % yellow
NH~
41 0 ~NH 98.3 % yellow
- 19 -
:......................................... . . . .
.,
` .
: ' .
1~lgZ~32
T a b 1 e 5
(Dyestuffs of the formula V)
E~mple ~ X ~ Yield Shade
42 ~ 97.2 ~ yellow
NHCO
43 ~ ~ 95.9 % orange
~ NHCONH ~
44 ~ ~ 98.7 % orange
~'
~ ~ 94.5 % greenish
yellow
2 ~ ~ yellow
-: ,
:, :
- - , : :.
.
