Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
2 0 ~ 3 ~
- 1
P-l 8133/A
Pervlenetetracarboxvlic acid diimides containin~ lon~-chain alkanoylamino radicals
The present invention relates to perylenetetracarboxylic acid diimides containing
long-chain cyclic or unsaturated alkanoylamino radicals which are attached to both
N-atoms through aromatic nuclei, and to the use thereof for colouring organic material of
high molecular weight.
N,N'-Dialkylperylene-3,4,9, 1 0-tetracarboxylic acid diimides containing long-chain alkyl
radicals for colouring polyolefins are disclosed in US patent specification 4 238 386.
These compounds are unsatisfactory on the one hand because of their tendency to
blooming and, on the other, because their wet~astness properties do not meet all the
current requirements of pigment technology.
Perylene-3,4,9,10-tetracarboxylic acid diirnides which are substituted at both N-atoms by
lower alkanoylamino groups, and the use thereof for colouring paints, coating materials
and plastics, are disclosed in US patent specification 2 462 851. These pigments too do not
meet all of the increasingly stringent requirements for specific applications.
lt is disclosed in EP-A û 283 436 that coloured polyolefins with enhanced properties can
be obtained by using peTylenetetracarboxylic acid diiTnides containing long-chain aliphatic
radicals which carry carboxyl or earbamoyl groups attached to both N-atoms.
There have now been found novel perylenetetracarboxylic acid diimides which contain
long-chain cyclic or unsaturated alkanoylamino radicals attached to both N-atoms through
aromatic nuclei and which, surprisingly, colour organic material of high molecular weight
in shades of enhanced fastness properties.
Specifically, the invention relates to compounds of formula
~ ~ 3 ?3
- 2 -
~ + I~lHCo ;~
wherein
R is C7-C21alkyl, C4-CI8alkenyl, C5-CI2cycloalkyl or Cs-C6cycloalkyl-substituted
Cl-C4alkyl,
Rl, R2, R3 and R4 are each independently of one another hydrogen, chloro, bromo, methyl
or methoxy,
Z is a direct bond or -O-, -S-, -N~-, -CO-, -SO2- or -NHCO-, and
n isOor 1.
R as C7-C21alkyl is s~raight-chain or branched alkyl and is typically n-heptyl, 1-, 2-, 3- s)r
4-methylhexyl, 1,1- or 3,4-dimethylpentyl, 1- or 3-ethylpentyl, 1,3,3- and
2,4,4-trimethylbutyl, 1-ethyl-3-methylbutyl, 1-propylbutyl, I-methyl-1-ethylbutyl,
1-propyl-2-methylpropyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, n-octyl, 2-, 3-,
4-, 5- or 6-methylheptyl, I,1-dimethylhexyl, 1,5-dimethylhexyl, 1-ethylhexyl,
1-ethyl-2-methylpentyl, 1-ethyl-1-methylpentyl, 1-ethyl-4-methylpentyl,
1-isopropylpentyl, 1,1,3,3-tetramethylbutyl, 2,2,3,3-tetramethylbutyl,
I-isopropyl-3-methylbutyl, nonyl, decyl, 1-neopentyl-3,3-dimethylbutyl, dodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, eicosyl or eneicosyl.
R as C4-Cl~alkenyl may also be straight-chain or branched alkenyl and is typically 1-, 2-
or 3-butenyl, I-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl,
2-methyl-1-propenyl, 1,3-butadienyl, 1-, 2-, 3- or 4-pentenyl, 1-methyl-1-butenyl,
3-methyl-1-butenyl, 3-methyl-2-butenyl, 1,3-pentadienyl, 3-methyl-1,3-butadienyl, 3- or
5-hexenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 4-methyl-3-pentenyl,
2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 1- or 6-heptenyl, 1-ethyl-1-pentenyl,
1-ethyl-2-pentenyl, 2,3,3-trimethyl-1-butenyl, 1- or 7-octenyl, 2-methyl-1-octenyl,
2-methyl-2-octenyl, ~-decenyl or 8-heptadecenyl.
- 2~ 33~
R as Cs-CI2cycloalkyl may be cyclopentyl, methylcyclopentyl, cyclohexyl,
methylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl.
R as Cs-C6cycloalkyl-substituted Cl-C4alkyl may be cyclopentylmethyl,
cyclohexylmethyl, cyclopentylethyl, cyclohexylpropyl, cyclopentylbutyl or
cyclohexylbutyl.
Particularly important compounds of formula I are those wherein n is 0 and, among these,
more particularly those compounds wherein Rl and R2 are hydrogen.
Preferred compounds are compounds of formula
~N ~I~HCO-R (Il)
wherein R is Cl2-Cl8alkyl.
The compounds of formula I can be prepared by methods which are sommonly known.
Conveniently they are obtained in two synthesis steps starting from perylene-3t4,9,10-
tetracarboxylic acid or the anhydride thereof, for example by an initial condensation with
an amino group of a diamine of ~orrnula
H2N $Z~NH2 (111),
R2 R4
- 4 -
wherein Rl, R2, R3, R4 and n are as defined above, and then by a second condensation of
the resultant diaminodiimide with a carbonyl chloride of formula
R-C\ ~IV),
wherein R is as defined above, in accordance with ~he following reaction scheme:perylene-3,4,9,10-tetracarboxylic acid or anhydride + at least
2 H2N--~Z~Nllz
~ R
+ at least
~0
2 R-C\
Cl
~f ~ ~3'~
- 5 -
~ ~ ~Z ~ NtlCO 1
The diamines of forrnula III are known compounds, most of which are commerciallyavailable.
:~ .
The carbonyl chlorides of formula IV can be conveniently prepared by known methods
~rom the corresponding known carboxylic acids, most of which are also commercially
available, typically by reaction with thionyl chloride. However, it is also possible to react
the free acid direct or a lower alkyl ester thereof.
The condensation reactions can be calTied out by comrnonly employed methods, forexample in the presence of an organic solvent or, if one of the reactants is used as solvent,
under normal or elevated pressure, with or without a catalyst.
Illustrative examples of suitable solvents for the initial condensation to form the
corresponding perylene diimides starting from perylene-3,4,9,10-tetracarboxylic acid or
the dianhydride thereof are water, dimethyl formamide, N-methylpyrrolidone, quinoline,
glycols such as ethylene glycol or propylene glycol, alcohols such as methanol, ethanol,
n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and its isomers or diacetone alcohol,
as well as aromatic hydrocarbons such as nitrobenzene, chlorobenzene, dichloro- and
trichlorobenzenes, toluene and xylenes.
Suitable solvents for the second condensation reaction are typically cyclohexane,
aromatic hydrocarbons such as nitrobenzene, chlorobenzene, dichloro- and
trichlorobenænes, toluene, xylenes, cumene and tert-butylbenzene.
,.....
~,~
2~3~
- 6 -
If one reactant is used direct as solvent (in excess) in the condensation reactions, then the
reaction medium is diluted, after complete amide formation, preferably with one of the
organic solvents cited above until the excess component is present in solution. The
residual suspension is then filtered, and the excess component can be recovered from the
filtrate by evaporation of the solvent.
A further means of preparing the compounds of formula I comprises condensing
perylene-3,4,9,10-tetracarboxylic dianhydride in general accordance with the commonly
employed methods described above with an amine of formula
H2N ~ NHCO R (V)
in the molar ratio 1:2.
The amines of forrnula V are known or they can be prepared by conventional methods.
The perylene diimides obtained in the practice of this invention are isolated and dried by
conventional methods. They h~sve excellent suitability as pigments for colouring organic
material of high molecular weight.
Illustrative examples of organic materials of high molecular weight which can be coloured
with the pigments of this invention are cellulose ethers and esters, such as ethyl cellulose,
nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins,
typically polymerisation or condensation resins, such as aminoplasts, preferablyurea/formaldehyde and melamine/formaldehyde resins, aLtcyd resins, phenolic plastics,
polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes,
polyesters, ABS, polyphenylene oxides, rubber, casein, silicone and silicone resins, singly
or in mixtures.
The above high molecular weight organic compounds may be singly or as mixtures in the
form of plastics, melts or of spinning solutions, paints, coating materials or printing inks.
Depending on the end use requirement, it is expedient to use the pigments of the invention
,
-- 2 ~
as ~oners or in the form of preparations.
The pigments of this invention are especially suitable for mass colouring polyvinyl
chloride and, preferably, polyole~lns such as polyethylene and polypropylene, as well as
for pigmenting paints and coating materials, more particularly automotive lacquers and,
among these, preferably metallic paints.
The pigments of the invention can be used in an amount of 0.01 so 30 % by weight,
preferably 0.1 to 10 % by weigh~ based on the high molecular weight organic material.
The pigmenting of the high molecular weight organic materials ~vith the pigments of this
invention is effected conveniently by incorporating the pigments by themselves or in the
form of masterbatches in the substrates using roll mills, mixing or milling apparatus. The
pigmented material is then brought into the desired final form by methods which are
known per se, conveniently by calendering, moulding, extruding, coating, spinning,
casting or by injection moulding. It is often desirable to incorporate plasticisers into the
high molecular weight compounds before processing in order to produce non-brittle
mouldings or to diminish their brittleness. Suitable plasticisers are typically esters of
phosphoric acid, phthalic acid or sebacic acid. The plasticisers may be incorporated before
or after working the pigments into the polymers. To obtain different shades it is also
possible to add fillers or other chromophoric components such as white, coloured or black
pigments, in any amount to the high molecular weight organic materials.
For pigmenting paints, coating materials and printing inks, the high molecular weight
organic materials and the pigments of the invention, together with optional additives such
as fillers, other pigments, siccatives or plasticisers, are ~1nely dispersed or dissolved in a
common organic solvent or solvent mixture. The procedure may be such that the
individual components by themselves, or also several jointly, are dispersed or dissolved in
the solvent and thereafter all the components are rnixed.
When used for colouring conveniently e.g. polyvinyl chloride or polyolefins, the pigments
of this invention have good general pigment properties, such as good dispersibility, high
colour strength and purity, as well as excellent fastness to migration, heat, light and
weathering. They have particularly good suitability for pigmenting paints for producing
metallic effect ~1nishes. In addition, they have excellent resistance to acid.
- 8 -
The invention is illustrated by the following Examples.
Example 1: 10 ml of pyridine are added to a mixture of 14.25 g of N,N'-bis(4-amino-
phenyl)perylenetetracarboxylic acid diimide and 27.75 g of stearoyl chloride in 500 ml of
o-dichlorbenzene, and the mixture is heated to 140C. The dark red suspension is stilred
for 6 hours at this temperature and afterwards cooled to 80C and filtered. The poduct is
washed in succession with 100 ml of o-dichlorobenzene, 1000 ml of hot alcohol and
1000 ml of hot water, and dried at 60C in a vacuum drier to give 25.55 g (92.4 % of
theory) of a red pigment of formula
~ N11CO~CHz)~jCH3
in powder form, which colours polyethylene, polyvinyl chloride and polyamide in strong
red shades of excellent fastness to migration, heat and light.
Analysis:
cal.: (in %): C 78.23 H 8.02 N 5.07
found: (in %): C 77.86 H 7.84 N 4.84.
Examples 2-16: Further pigments can be prepared by the method described in Example 1
by acylating each of the diarnines listed in column I of the following Table with the acid
chloride listed in column II in the molar ratio 1:2. Column III indicates ~he shade of the
PVC sheet coloured with the resultant pigments in accordance with subsequent
Example 17.
~d ~3~
g
Ex. II III
2 N,N'-bis(4-aminophenyl)perylene- decanoyl chloride red
tetracarboxylic acid diimide
3 N,N'-bis(4-aminophenyl)perylene- 3-cyclopentylpropionyl orange red
tetracarboxylic acid diimide chloride
4 N,N'-bis(4-aminophenyl)perylene- lauroyl chloride red
tetracarboxylic acid diimide
N,N'-bis(4-aminophenyl)perylene- undecanoyl chloride red
tetracarboxylic acid diimide
6 N,N'-bis(4-aminophenyl)perylene- tetradecanoyl chloride red
tetracarboxylic acid diimide
7 N,N'-bis(4-aminophenyl)perylene- heptanoyl chloride red
tetracarboxylic acid diimide
8 N,N'-bis(4-aminophenyl)perylene- octanoyl chloride red
tetracarboxylic acid diimide
9 N,N'-bis(4-aminophenyl)perylene- pelargonyl chloride orange red
tetracarboxylic acid diimide
N,N'-bis(4-arninophenyl)perylene- palmitoyl chloride red
tetracarboxylic acid diimide
11 N,N'-bis(4-aminophenyl)perylene- 10-undecenoyl chloride dark red
tetracarboxylic acid diimide
12 N,N'-bis(4-aminophenyl)perylene- oleyl chloride red
tetracarboxylic acid diimide
13 N,N'-bis(2,5-dimethyl-4-amino- stearoyl chloride orange
phenyl)perylenetetracarboxylic
acid diimide
14 N,N'-bis(2,5-dimethyl-4-amino- lauroyl chloride orange
phenyl)perylenetetracarboxylic
acid diimid
N,N'-bis(2,5-dirnethyl-4-amino- oleyl chloride orange
phenyl)perylenetetracarboxylic
acid diimide
16 N,N'-bis(3-aminophenyl)perylene- lauroyl chloride red
tetracarboxylic acid diimide . _
- lo -
Example 17: 40 mg of the perylene diimide pigment according to Example 1,7.3 rnl of
dioctyl phthalate and 13.3 g of stabilised polyvinyl chloride (~)LONZA E-722 arethoroughly mixed in a glass beaker with a glass rod, and the mixture is processed to a thin
sheet on a roll mill for 5 minutes at 160C. The PVC sheet so obtained is coloured in a
strong red shade of high purity and very good lightfastness. The dispersibility of the
pigment is excellent.
Example 18: A mixture of 1.0 g of the perylene diimide pigment obtained according to
Example 1, 1.0 g of antioxidant ~)IRGANOX 1010 (CIBA-GEIGY AG) and 1000 g of HD
polyethylene granules ((~)VESTOLEN A60-16, HUELS) is stirred for 15 minutes in a3 litre glass bottle on a roller gear table. The mixture is then extruded in two passes in a
single screw extruder. The granulate so obtained is moulded to boards at 250C in an
injection moulding machine ((~)Allround Aarburg 200)for 5 minutes. The mouldings are
coloured in a strong, level red shade of high purity and excellent lightfastness.
Example 19: 1000 g of polypropylene granules (~DAPLEN PT-55, Chernie LINZ) and
1.0 g of the perylene diimide pigment obtained according to Exarnple 1 are rnixed for
15 minutes in a 3 litre bottle on a roller gear bed. The mixture is subsequently extruded
twice through a single-screw extruder and then granulated. The granules so obtained are
spun at 280-285C by the melt spinning process. The red filaments have very goodlightfastness and excellent textile properties, such as rubfastness and wetfastness to
detergents and solvents. The pigment has excellent heat resistance during the spinning
process at 285C.
Example 20: The process described in Example 18 is repeated, but using, in addition to the
coloured pigment, 10 g of titanium dioxide ~KRONOS RN-57-P (KRONOS Titan
GmbH), to give red pressed sheets having comparably good heat resistance. The pressed
sheets, which are injection moulded at 200-2oOC, exhibit no colour deviations after
cooling.
Example 21: A mixture of
130 g of steatite balls (0 = 8 mm),
45.5 g of a thermosetting acrylic varnish consisting of
41.3 g of acrylic resin ~g)VIACRYL VC 373, 60 % (VIANOVA Kunstharz AG),
2 0 ~
16.3 g of melamine resin (~)MAPRENAL l'rX, 55 % (HOECHST AG),
32.8 g of xylene,
4.6 g of ethyl glycol acetate,
2.0 g of butyl acetate and
1.0 g of (~)silicone oil A, 1 % in xylene (BAYER AG), and
2.5 g of the perylene diimide obtained in Example I
is dispersed in a 200 ml glass bottle with twist-off stopper for 72 hours on a roller gear
bed. The steatite balls are removed and then 8.0 g of the dispersed masstone mixture, 0.6 g
of alun~inium paste ~ALCOA, (60-65 % Al content, Aluminium Corp. of America), 1.0 g
of methyl ethyl ke.one and 18.4 g of the above therrnosetting acrylic varnish are
thoroughly mixed, and the mixture is sprayed on to alurninium sheets and subsequently
baked for 30 minutes at 130C, to give very strong red metallic effect finishes of excellent
fastness properties.
