Compositions: coating or plastic – Materials or ingredients – Pigment – filler – or aggregate compositions – e.g. – stone,...
Reexamination Certificate
2001-07-27
2002-10-29
Green, Anthony J. (Department: 1755)
Compositions: coating or plastic
Materials or ingredients
Pigment, filler, or aggregate compositions, e.g., stone,...
C106S493000, C106S495000, C106S496000, C106S497000, C106S498000, C430S007000, C430S270100, C524S090000
Reexamination Certificate
active
06471765
ABSTRACT:
The present invention relates to compositions comprising a sulfonated diketopyrrolopyrrole and a Mannich-type substituted dihydroquinacridone. Such compositions are excellently suitable for dispersing fine-sized pigments (especially diketopyrrolopyrrole pigments) into polymers. They lead to pigmentations of increased stability at high temperatures.
Pigments of very fine particle size are difficult to disperse in polymers, and at high concentrations they lead to high viscosity and poor workability of the pigmented polymers. This is especially the case for diketopyrrolopyrrole pigments. There have been some attempts to solve this well-known problem by using additives, for example dispersants, rheology improvers and/or so-called synergists—whatever is meant therewith.
JP-A-06/145546 discloses phthalimidomethyl dihydroquinacridones and the use thereof as pigment dispersants. Some examples disclose their use for Pigment Red 254 or Pigment Violet 19, in further combination with ®BYK 160, which is a basic resin.
GB-B-2 238 550 discloses sulfonated diketopyrrolopyrrole mixtures and the use thereof as rheology improvers for diketopyrrolopyrrole pigments. Such a composition is commercially available for use in colour filters since 1997 as Irgaphore® Red BT-CF. Its use in liquid crystal displays is disclosed in JP-A-2000/160084.
However, the results obtained hitherto are still not entirely satisfactory. In particular, known pigment compositions undergo particle growth when incorporated into a polymer and heated to high temperatures. Thus, the transparency decreases and there are changes in hue, chroma and lightness. This is particularly problematic in the manufacture of colour filters.
Surprisingly, the instant compositions lead to a much improved heat stability. The optical and coloristic properties persist to a very satisfactory degree even when the pigmented material is heated to high temperatures. The instant compositions are also easier to make and to use with pigments, as the components can simply be mixed, without requiring special treatments.
The present invention relates to a composition comprising:
(a) a compound of formula
in which
R
1
and R
2
are independently from each other H, F, Br, Cl, C
1
-C
3
alkyl and C
1
-C
3
alkoxy;
R
3
is a group (SO
3
−
M
+
)
m
wherein M
+
is H or a metal or ammonium cation and m is a number from zero to 2.5; and
R
4
is a group
which can be unsubstituted or substituted by 1 to 3 groups halogen, oxy, hydroxy, C
1
-C
3
alkoxy, SO
3
−
M
+
or CO
2
−
M
+
, wherein X
1
to X
4
are independently from each other CO, NR
5
, O, S or SO
2
, and/or X
1
and X
2
together, X
2
and X
3
together or X
3
and X
4
together are
and R
5
to R
7
are independently from each other H, OH, C
1
-C
3
alkoxy or C
1
-C
3
alkyl or R
6
and R
7
together with —C═C— form an aromatic or heteroaromatic group; and
(b) a sulfonated diketopyrrolopyrrole.
The nature of M
+
is not essential, as M
+
can easily be exchanged in the application. A metal M in formula (I) can for example be selected from IUPAC groups 1, 2, 3, 4 or 13. Preferably, M is sodium, potassium, calcium, magnesium or aluminum. When the metal forms cations with more than one positive charge, its stoichiometric amount should be calculated accordingly, for example 1/2 Ca
++
or 1/3 Al
+++
for 1 M
+
.
M
+
as an ammonium cation in formula (I) is for example NH
4
+
or a primary, secondary, tertiary or quaternary ammonium salt, the substituents of which can be for example C
1
-C
30
alkyl, C
5
-C
6
cycloalkyl, C
7
-C
30
arylalkyl or C
6
-C
18
aryl, which can further be substituted by hydroxy or oxa groups, such as in polyalkylene oxy chains. Two substituents together can also for example form a ring, for example in pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline. Preferably, the ammonium cation is NH
4
+
or C
1
-C
30
alkyl ammonium.
Examples of groups
are pyrrolo, imidazolo, pyrazolo, indolo, isoindolo, indazolo, purino, carbazolo, perimidino, phenothiazino, phenoxazino or phthalimido. Aromatic or heteroaromatic groups
are for example phenylen, naphthylen, pyridylen, pyrazinylen, pyrimidinylen or pyridazinylen.
Most preferred group
Preferably, m is 0 or 1, most preferably 0. Compounds of formula (I), can very conveniently be used also in the form of mixtures, wherein m is in average preferably from 0.0 to 0.5, most preferred from 0.0 to 0.1.
R
1
and R
2
are preferably both H and R
4
is preferably unsubstituted.
The compounds of formula (I) are known or can be prepared in close analogy to known methods, such as the method disclosed in EP-A-1 026 207.
The most preferred component (a) is of formula
Sulfonated diketopyrrolopyrroles can for example be either pure compounds having 1 or 2 sulfonate groups or mixtures thereof, or preferably mixtures consisting of unsubstituted diketopyrrolopyrroles and sulfonated diketopyrrolopyrrole derivatives thereof having 1 or 2 sulfonate groups. Generally, such products or mixtures are easily obtained by sulfonating diketopyrrolopyrrole pigments as disclosed below. Depending on the conditions which are known per se, the pigment particles are entirely sulfonated and disappear, or only some particles are entirely sulfonated and disappear, or the particles are only sulfonated on their surface. The latter case is preferred, whereby the apparent number of sulfonate groups per molecule of pigment can also be less than 1.
In the absence of other substituents, sulfonation of diketopyrrolopyrroles generally leads to derivatives sulfonated in para position.
Preferred sulfonated diketopyrrolopyrrole (b) is a compound of formula
wherein R
8
and R
9
are each independently of the other hydrogen, halogen, cyano, carbamoyl, nitro, trifluoromethyl, phenyl, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
1
-C
6
alkylthio or C
1
-C
6
alkylamino, M
+
is H or a metal or ammonium cation and n is a number from 0.1 to 2, more preferably from about 0.2 to about 1.0, most preferably about 0.6 to about 0.7.
Particularly preferred sulfonated diketopyrrolopyrroles (b) are such obtained from Colour Index Pigment Orange 71, Pigment Orange 73, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, 3,6-di(4′-cyano-phenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrol-1,4-dione, 3,6-di(3,4-dichloro-phenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrol-1,4-dione or 3-phenyl-6-(4′-tert.-butyl-phenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrol-1,4-dione. Suitable sulfonation methods are known in the art.
Most preferred are compounds of formula (III), wherein R
8
and R
9
are independently from each other H or Cl, and also mixtures thereof. M
+
is most preferably Na
+
, 1/2 Ca
++
or NH
4
+
.
The instant compositions preferably also comprises as an additional component (c) an organic pigment, preferably a polycyclic pigment, most preferably a diketopyrrolopyrrole pigment.
Preferably, component (c) is a pyrrolo[3,4-c]pyrrole of formula
wherein G and Q are each independently of the other a group of formula
wherein R
8
and R
9
are each independently of the other hydrogen, halogen, cyano, carbamoyl, nitro, trifluoromethyl, phenyl, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
1
-C
6
alkylthio or C
1
-C
6
alkylamino.
Particularly preferred components (c) are Colour Index Pigment Orange 71, Pigment Orange 73, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, 3,6-di(4′-cyano-phenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrol-1,4-dione, 3,6-di(3,4-dichloro-phenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrol-1,4-dione oder 3-phenyl-6-(4′-tert.-butyl-phenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrol-1,4-dione. Most preferred is Pigment Red 254.
The weight ratio of component (a) to component (b) is preferably from 5:95 to 95:5, more preferably from 20:80 to 80:20, most preferably from 40:60 to 60:40.
When the composition also comprises a component (c), the amount of components (a) and (b) together is preferabl
Ciba Specialty Chemicals Corporation
Crichton David R.
Green Anthony J.
LandOfFree
Dispersant compositions improving the heat stability of... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Dispersant compositions improving the heat stability of..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Dispersant compositions improving the heat stability of... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2928143