Perylene-derivative based crystallization modifiers

Details Perylene-derivative based crystallization modifiers Perylene-derivative based crystallization modifiers

2002-09-11

2004-08-31

Aulakh, Charanjit S. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C106S493000, C106S494000, C106S506000, C106S275000

Reexamination Certificate

active

06784301

ABSTRACT:

The present invention relates to perylene derivatives of the general formula I
where
X and Y are independently oxygen, —NR
1
or —NR
2
;
R
1
and R
2
are independently hydrogen, C
1-C
18
-alkyl, C
5-C
7
-cycloalkyl, aryl or C
1-C
6
-alkoxy;
R
3
to R
10
are independently hydrogen, hydroxyl or aryl, although radicals conjointly attached to one carbon atom may also be ═O or ═CHR
11
,
R
11
is hydrogen or C
1
-C
3
-alkyl,
with the proviso that said perylene derivative I contains from at least one to not more than three carbonyl groups per molecule.
This invention also relates to the use of perylene derivatives I as crystallization modifiers for organic pigments and also to pigment preparations comprising the perylene derivatives I.
Perylene pigments are well known. They are notable for their high color strength and light- and weatherfastnesses and are of major importance for paint and plastics coloration. As examples of particularly interesting representatives of this class of pigment there may be mentioned N,N′-dimethylperylene-3,4,9,10-tetracarboxylic diimide (C.I. Pigment Red 179), N,N′-bis(4-phenylazophenyl)perylene-3,4,9,10-tetracarboxylic diimide (C.I. Pigment Red 178 and N,N′-bis(3,5-dimethylphenyl)-perylene-3,4,9,10-tetracarboxylic diimide (C.I. Pigment Red 149).
However, the synthesis of these pigments gives rise to crude pigments having a technically unfavorable particle shape and size, which are in need of an aftertreatment, for example as described in DE-A-21 53 087, or a salt grinding or kneading operation in order that they may be converted into a useful pigmentary form.
It is also known to add substances to influence the crystallization of the crude pigment and promote the formation of transparent pigments. For instance, in EP-A-807 668 the crude pigment is for this purpose subjected to an acid swell in the presence of anthanthrone, quinacridone and flavanthrone pigments. WO-A-91/02034 describes dispersants which are based on perylene-3,4,9,10-tetracarboxylic monoanhydride monoimides or diimides substituted by alkylene- or arylene-sulfonic acid groups on either or both imide nitrogen atoms, and which coat the pigment surface. However, these pigment preparations have different color properties as a result of the added pigment, or have only limited utility.
It is an object of the present invention to provide crystallization modifiers that will provide transparent perylene pigments having excellent application and color properties.
We have found that this object is achieved by the perylene derivatives of the formula I defined at the outset and by their use as crystallization modifiers for organic pigments.
The present invention further provides pigment preparations comprising
A) at least one organic pigment from the class of the perylene pigments and
B) at least one perylene derivative of the formula I and optionally
C) at least one rosin.
Any alkyl appearing in the formula I may be straight-chain or branched. It contains up to 18 carbon atoms, although C
1
-C
4
-alkyl radicals, especially methyl, are preferred. Specific examples are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl (the above designations isooctyl, isononyl, isodecyl and isotridecyl are trivial names derived from the alcohols obtained by the oxo process).
Useful cycloalkyl radicals are cyclopentyl, cyclohexyl and cycloheptyl.
Examples of useful aryl radicals include as well as &agr;- and &bgr;-naphthyl especially phenyl and substituted phenyl such as 4-phenylazophenyl and alkyl-substituted phenyl, eg. 3,5-dimethylphenyl, which alongside C
1
-C
4
-alkyl are preferred meanings of R
1
and R
2
.
Any alkoxy appearing in the formula I may likewise be straight-chain or branched. Examples are methoxy, ethoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxy and hexoxy.
Preference is given to perylene derivatives of the formula I where the R
5
and R
6
pair and the R
7
and R
8
pair are each ═O, i.e. perylene derivatives that contain at least two carbonyl groups.
Particular preference is given to perylene derivatives of the formula I where R
3
, R
4
, R
9
and R
10
are each hydrogen or hydroxyl, although the R
3
and R
4
pair or the R
9
and R
10
pair can also be ═O, and the R
5
and R
6
and the R
7
and R
8
pairs are each ═O.
Preferably in this context only one in each pair of radicals bonded to one carbon atom is hydroxyl.
Examples of very particularly preferred perylene derivatives are:
Perylene
derivative
X
Y
R
3
, R
4
R
5
, R
6
R
7
, R
8
R
9
, R
10
Ia
O
O
OH, H
═O
═O
H, H
Ib
O
O
═O
═O
═O
H, H
Ic
O
O
H, H
═O
═O
H, H
Id
NCH
3
NCH
3
═O
═O
═O
H, H
Ie
NCH
3
NCH
3
OH, H
═O
═O
═O
If
O
NCH
3
H, H
═O
═O
H, H
Ig
NCH
3
O
OH, H
═O
═O
═O
Ih
NC
2
H
5
O
OH, H
═O
═O
═O
Ik
NCH
3
NCH
3
H, H
═O
═O
H, H
Im
O
O
═CH
2
═O
═O
═O
In
O
NCH
3
═CH
2
═O
═O
═O
Particular emphasis is in this connection given to the perylene derivatives Ia, Ib, Ie and Ik.
The perylene derivatives I according to the invention may be prepared starting from perylene-3,4,9,10-tetracarboxylic anhydride, N-substituted or unsubstituted perylene-3,4,9,10-tetracarboxylic monoanhydride monoimides or N,N′-substituted or unsubstituted perylene-3,4,9,10-tetracarboxylic diimides as reactants.
Reduction of these reactants is an advantageous way to obtain the particularly preferred perylene derivatives of the formula I where R
3
, R
4
, R
9
and R
10
are each hydrogen or hydroxyl, although the R
3
and R
4
pair or the R
9
and R
10
pair can also be ═O, and the R
5
and R
6
and the R
7
and R
8
pairs are each ═O.
The reducing agents used for this reduction are preferably complex hydrides of the general formula II
M
1
(M
2
H
m
R′
n
)
p
  II
where
M
1
is a p-valent metal cation such as lithium, sodium, magnesium or aluminum;
M
2
is boron or aluminum subject to the proviso that M
1
≠M
2
;
R′ is alkyl or alkoxy or, when M
2
is boron, cycloalkyl containing the boron atom in the ring;
m is from 1 to 4;
n is from 0 to 3 subject to the proviso that m+n 4;
p is from 1 to 3.
Examples of useful hydrides II are LiBH
4
, NaBH
4
, LiAlH
4
, NaAlH
4
, Mg(BH
4
)
2
, Al(BH
4
)
3
, LiAlH[OC(CH
3
)
3
]
3
, NaAlH
2
(C
2
H
5
)
2
and NaAlH
2
(OC
2
H
4
OCH
3
)
2
. Of these, sodium borohydride and lithium aluminum hydride are preferred.
The reaction with the hydride II can be carried out in aqueous phase or in an organic solvent.
When sodium borohydride is used, a particularly useful reaction medium is water or a dipolar aprotic solvent that does not react with the hydride, eg. dimethyl sulfoxide, N-methylpyrrolidone or dimethylacetamide.
When lithium aluminum hydride is used, it is preferable to use an apolar aprotic solvent, for example tetrahydrofuran or diethyl ether.
Specific selection of the reaction conditions (amount of hydride II, reaction temperature and reaction time) provides trouble-free control over the reduction.
This will now be illustrated using the perylene derivatives Ia to Ic according to the invention as an example. They are advantageously preparable from perylene-3,4,9,10-tetracarboxylic dianhydride as follows:
Since in the case of these perylene derivatives I only one side of the molecule is to be reduced, it is advisable first to convert the perylene-3,4,9,10-tetracarboxylic dianhydride into the monopotassium salt, which additionally possesses higher solubility. This, after intermediate isolation or directly, can be reacted with the hydride II (eg. sodium borohydride, amount based on 1 g of perylene-3,4,9,10-tetracarboxylic dianhydride) under the conditions set out hereinafter:
0.9-1.1 g of h

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