U.S. patent application number 10/887494 was filed with the patent office on 2004-12-16 for pigments having improved colouristic properties and process for their preparation.
Invention is credited to Deno, Takashi, Grandidier, Yves, Riegler, Albert, Ruf, Klaus, Schlatter, Urs.
Application Number | 20040250733 10/887494 |
Document ID | / |
Family ID | 4206713 |
Filed Date | 2004-12-16 |
United States Patent
Application |
20040250733 |
Kind Code |
A1 |
Grandidier, Yves ; et
al. |
December 16, 2004 |
Pigments having improved colouristic properties and process for
their preparation
Abstract
The invention relates to a process for preparing pigments, which
comprises subjecting a crude pigment or mixture of crude pigments
and a crystalline inorganic salt or mixture of crystalline
inorganic salts together, essentially in the absence of other
constituents, to the action of a rotor having a tangential speed of
at least 10 m/s, so that a temperature of at least 80.degree. C. is
attained by means of friction effects; and subsequently kneading
the product of this treatment with an organic liquid, during which
it is possible if desired to add additional substances selected
from the group consisting of inorganic salts, inert additives and
colorants. These pigments and their use in polymers, printing inks
and colours filters are also claimed. The invention in particular
relates to a novel pigment form of Pigment Violet 23 1 obtained by
above-mentioned process and having higher colour strength and
colour saturation as well as excellent other applications
properties in particular in printing inks. The invention also
relates to a highly crystalline novel form of Pigment Red 254 2
obtained by above-mentioned process, too, and having a steep slope
on the bathochromic side of the absorption spectrum's maximum, and
the use thereof in particular in colour filters.
Inventors: |
Grandidier, Yves; (Rosenau,
FR) ; Riegler, Albert; (Basel, CH) ; Ruf,
Klaus; (Bollschweil, DE) ; Schlatter, Urs;
(Prattlen, CH) ; Deno, Takashi; (Nishinomiya-shi,
JP) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
4206713 |
Appl. No.: |
10/887494 |
Filed: |
July 8, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10887494 |
Jul 8, 2004 |
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10309740 |
Dec 4, 2002 |
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10309740 |
Dec 4, 2002 |
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09611815 |
Jul 7, 2000 |
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6517630 |
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Current U.S.
Class: |
106/410 ;
106/493; 106/494; 106/495; 106/496; 106/497; 106/498 |
Current CPC
Class: |
C09B 67/0002 20130101;
C09B 67/0001 20130101; C09B 67/0014 20130101; C09B 67/0022
20130101 |
Class at
Publication: |
106/410 ;
106/493; 106/494; 106/495; 106/496; 106/498; 106/497 |
International
Class: |
C09B 067/50; C08K
005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 9, 1999 |
CH |
1279/99 |
Claims
1-19. (cancelled).
20. A 1,4-diketopyrrolo[3,4c]-pyrrole pigment, characterized in
that a 50% by weight dispersion thereof in a methacrylic resin,
applied as a film of thickness such that the absorption maximum in
the area from 400 to 700 nm has an intensity of 1.0.+-.0.1, the
maximum slope on the bathochromic side of the absorption maximum in
the range from 500 to 650 nm reaches at least a 5% change in
absorption per 1 nm change in wavelength, based on the absorption
at said absorption maximum.
21-27. (cancelled).
Description
[0001] The invention relates to a novel pigment form of Pigment
Violet 23, having a higher colour strength and higher colour
saturation as well as excellent other applications properties. The
pigment of the invention is obtained by kneading an amorphized form
with an inorganic salt in the presence of an organic liquid and may
be used in particular in printing inks. By using the same
procedure, it is also possible to improve the applications
properties of other pigments, amongst them in particular Pigment
Red 254.
[0002] Shade, colour strength, gloss and transparency are the most
important colouristic properties in printing inks and colour
filters. The shade must correspond to very specific values but with
maximum possible colour saturation with a view to a broad colour
palette in multicolour printing. To this end, the colour strength,
gloss and transparency should be as high as possible.
[0003] Additionally, pigments should nowadays be able to be used
without losses in their applications properties even in modern,
environmentally friendly systems, for example in water-based
coating compositions or printing inks. These are formulations whose
volatile fraction consists of from 5 to 100% by weight, preferably
of at least 20% by weight, with particular preference of at least
50% by weight, of water, based on the overall weight of all
volatile components.
[0004] C.I. Pigment Violet 23 [51319, "Carbazole Violet"] is an
important commercial pigment which is available in many grades, for
example as Cromophtal.RTM. Violet GT (Ciba Spezialitaten-chemie
AG), Hostaperm.RTM. Violet RL Special (Clariant) or Fastogen.RTM.
Super Violet RN (Dainippon Ink). However, it has been found that
none of the products known to date is capable of giving complete
satisfaction, especially as regards colour strength, colour
saturation, gloss and transparency in the case of printing ink
applications.
[0005] C.I. Pigment Red 254 [56110], the first and most important
commercial 1,4-diketopyrrolo-[3,4c]-pyrrole pigment, is also
available in many different grades such as for example Irgazin.RTM.
Red BO or Irgaphor.RTM. Red B-CF (Ciba Specialty Chemicals Inc.).
However, their coloristic properties, especially the hue and
transparency, have proven still not to reach perfectly the desired
values.
[0006] U.S. Pat. No. 5,281,268 discloses a process for the
manufacture of .beta.-form copper phthalocyanine, wherein the crude
is first dry-milled with an attriter under unknown speed
conditions, then wet-milled with a kneader in the presence of an
inorganic salt and an organic solvent. This pigment has excellent
gloss and clearness in colours inks, coatings and coloured plastic
articles.
[0007] U.S. Pat. No. 3,598,625 discloses a pigment preparation
process, directed primarily also to copper phthalocyanine, in which
the crude pigments are first subjected to forces of wear and shear,
then treated with micropulverized salt and a solvent in a mixer. In
one example, after grinding, Pigment Violet 23 is treated with 9
times the amount of salt and 1.1 times the amount of hexylene
glycol. The proportion of hexylene glycol to the crystalline
inorganic salt is 1 ml: 7.54 g, that of hexylene glycol to salt
plus pigment is 1 ml: 8.38 g.
[0008] However, it later became evident, from a variety of sources,
that the destruction of the crystallinity in the case of dioxazine
pigments is disadvantageous and to be avoided.
[0009] Thus U.S. Pat. No. 4,253,839 discloses that coarse-particled
dioxazine pigments should be ground in such a way that their
crystal structure is essentially retained. Since this grinding
process leads to defective surfaces, it absolutely must be
supplemented, moreover, by aftertreatment with a solvent, which
always takes place in the presence of an acid, a base or a
resin.
[0010] Better results are obtained in accordance with U.S. Pat. No.
5,800,607 if crude Pigment Violet 23 is ground at high peripheral
speed in a nonflocculating liquid medium, especially glycols and
their ethers.
[0011] U.S. Pat. No. 4,804,417 describes the treatment of crude
dioxazine violet with sulfuric acid, followed by treatment in an
aqueous medium comprising a dissolved inorganic salt and small
amounts of an alcohol, which gives pigments having a very high
specific surface area. Crystal growth is not intended to take
place.
[0012] EP 069 895 discloses the conditioning of crude polycyclic
pigments, including Pigment Violet 23, by grinding with sodium
sulfate, sodium chloride or aluminium sulfate in the presence of a
glycol and an alkaline earth metal halide. This is intended to
achieve improved transparency, a cleaner hue and a greater colour
strength.
[0013] Similar advantages are achieved, however, in accordance with
EP 075 182 in the conditioning of an organic pigment by treatment
with polyphosphoric acid, Pigment Violet 23 again being
mentioned.
[0014] According to DE 1 225 598, after dry grinding, dioxazine
violet is ground further with aliphatic, araliphatic or aromatic
nitro compounds, for example with nitrobenzene. However, there are
no inorganic salts present.
[0015] U.S. Pat. No. 5,194,088, on the other hand, describes a
process for conditioning pigments wherein the crude products are
first of all preground, then simply contacted with a highly polar
solvent at a temperature below 50.degree. C. Pigment Blue 60 and
Pigment Violet 37 produce colour strengths and colour saturations
which correspond approximately to those of existing products.
Pigment Violet 23 is not mentioned, Pigment Red 254 only as the
minor component of a solid solution into Pigment Red 202.
[0016] U.S. Pat. No. 4,785,999 describes an analogous process
wherein a very specific grinding mechanism is used and the
aftertreatment takes place in a very large amount of solvent.
Disclosed among many other solvents are ketones, esters and
dimethylformamide. Pigment Violet 23 of purportedly excellent
colour strength and dispersibility is said to be obtainable in this
way if the aftertreatment takes place in a xylenetwater
emulsion.
[0017] U.S. Pat. No. 5,626,662 and JP 09/165528 disclose processes
in which pigments are first dry-ground and then ground in aqueous
suspension in a powerful, high-speed ball mill.
[0018] EP 780 446 discloses the single-stage conversion of crude
dioxazine violet into a strongly coloured, pure pigmentary form by
means of salt grinding with 2-ethylcaproic acid.
[0019] U.S. Pat. No. 4,317,908 discloses a process for preparing
the p crystal form of Pigment Violet 23 in a two-phase mixture of
water and an aromatic compound.
[0020] U.S. Pat. No. 5,476,949 discloses finely divided highly
transparent diketopyrrolopyrrole pigments of high chroma (CIELAB
C*) and outstanding transparency. These pigments are obtained
directly from the reaction of succinates with nitrites in a molar
ratio of 1:2.
[0021] All of these extremely diverse methods, however, have still
been unable fully to unlock the hitherto unsuspectedly high
colouristic potential of pigments such as particularly Pigment
Violet 23 and Pigment Red 254.
[0022] It has now been found, completely unexpectedly, that a
violet pigment having improved colouristic properties and
surprisingly higher colour strength may indeed be obtained by
grinding amorphized Pigment Violet 23 with an inorganic salt in the
presence of an organic liquid if the organic liquid used contains
oxo groups and the ratio of Pigment Violet 23 and inorganic salt to
the organic liquid, and the temperature, are chosen so as to give a
kneadable composition.
[0023] A pigment having hitherto unattained colouristic properties
is obtained which is ideally suited to all applications, especially
for printing inks, preferably for water-based printing inks.
[0024] The invention therefore provides a pigment of the formula
3
[0025] which, measured in gravure printing with an applied amount
after drying of 0.860 g/m.sup.2, of which pigment of the formula
(I) accounts for 0.068 g/m.sup.2, printed on white kraft paper,
gives after drying a lightness L* of not more than 48, a chroma C*
of at least 53 and a hue angle h of from 295 to 315,
[0026] the gravure printing ink being prepared by dispersing 30
parts by weight of pigment and 30 parts by weight of an aqueous
solution containing 30% by weight of a dispersing resin dissolved
therein and 7% by weight of isbpropanol, based in each case on the
weight of the solution, first with a laboratory dissolver at 6000
rpm and 23.+-.2.degree. C., for 15 minutes, then in a bead mill
with ceramic beads of diameter 1.1.+-.0.1 mm at 6000 rpm and
30.+-.10.degree. C., for 10 minutes, and diluting the resulting
dispersion with 900 parts by weight of an aqueous solution
containing 18% by weight of a polyacrylate dissolved therein and
15% by weight of isopropanol, based in each case on the weight of
the solution, in a laboratory dissolver at 6000 rpm and
23.+-.2.degree. C. for 15 minutes.
[0027] The structure (I) was assigned to Pigment Violet 23 in
accordance with the Ullmann encyclopaedia.
[0028] The lightness L* is preferably not more than 47.5, with
particular preference not more than 47, with very particular
preference not more than about 46.5. The chroma C* is preferably at
least 53.5, with particular preference at least 54. The hue angle h
is preferably from 305 to 312, with particular preference from 307
to 310, with very particular preference from 308 to 309.
[0029] The lightness L* is situated in general between a minimum
value of about 40 and the maximum value specified above, usually
between a minimum value of about 44 and the maximum value specified
above. The chroma C* is situated in general between the minimum
value specified above and a maximum value of about 60, usually
between the minimum value specified above and a maximum value of
from about 56 to 57.
[0030] The colour values are understood as corresponding to the CIE
standard 1976 and measured under illumination with standard
illuminant D65 and a 10.degree. standard observer, using the
visible range from 400 to 700 nm. The white kraft paper itself
should be used as the white standard for calibrating the measuring
instrument. For examining the colour values, the most suitable
paper is a white kraft paper having a nominal weight of from 120 to
150 g/m.sup.2, in particular approximately 135 g/m.sup.2, which
contains no optical brightener. For example, use may be made of
Zanders.TM. Mega Web 135gr no. 585585 (Sihl & Eika Papier AG,
CH-8800 Thalwil, Switzerland).
[0031] In case of doubt, the colour values should be determined in
accordance with the procedure specified in Example D1 below.
[0032] The pigment may be pure or may in addition to the
chromophore of the formula (I) contain further components, examples
being customary pigment binders or dispersants, which are known to
the skilled worker. Additional components are preferably
colourless, only weakly coloured, or of the same colour as the
chromophore of formula (I), so that they do not substantially
influence the colour values of the pigment. If appropriate, in a
colour print, further components whose specific absorption
coefficient is less than 30% of the specific absorption coefficient
of the pigment of the formula (I) at its absorption maximum are
taken into account in the overall solids content but not in the
pigment content.
[0033] It is also possible to surface-modify the pigment of the
invention in accordance with one of the many known methods, in
order, for example, to increase its dispersibility.
[0034] The invention further provides a process for preparing the
pigment of the invention, described above, by kneading a
composition consisting essentially of a compound of the formula
(I), a crystalline inorganic salt or mixture of crystalline
inorganic salts and an organic liquid, wherein
[0035] at the beginning of kneading, the compound of the formula
(I) is in substantially amorphous form;
[0036] the organic liquid contains at least one oxo group in its
molecule; and
[0037] the proportion of organic liquid to inorganic salt is from 1
ml: 6 g to 3 ml: 7 g, and the proportion of organic liquid to the
overall weight of inorganic salt and compound of the formula (I) is
from 1 ml: 2.5 g to 1 ml: 7.5 g.
[0038] The weight ratio of compound of the formula (I) to
crystalline inorganic salt is preferably from 1:4 to 1:12. The
temperature is judiciously from -20 to just below the boiling point
of the organic liquid, in particular up to about 100.degree. C.
[0039] The substantially amorphous nature of the compound of the
formula (I) is recognized by the skilled worker in accordance with
his or her general knowledge; for example, from the flat X-ray
diffraction diagram. If use is made of the X-ray index defined in
U.S. Pat. No. 4,253,839, then this index should be judiciously less
than 4, preferably less than 2, with particular preference from 0
to 1.5.
[0040] A method which has proved particularly effective for
efficiently reducing the degree of crystallinity is a novel method
in which the crude pigment is subjected, together with an inorganic
salt, to very high acceleration. Surprisingly, significantly better
results are achieved than in the absence of the inorganic salt or
in the case of customary, lower acceleration.
[0041] The invention therefore also provides a process for
converting a crude pigment into an substantially amorphous
fine-particled form, which comprises subjecting a crude pigment and
a crystalline inorganic salt or mixture of crystalline inorganic
salts together, essentially in the absence of further components,
to the action of a rotor having a-tangential speed of at least 10
m/s, so that by means of friction effects a temperature of at least
80.degree. C. is reached.
[0042] Mixers known as high-speed mixers or heating mixers are
known per se to the skilled worker. They comprise a static
container with one or more rotors which may be operated at high
rotational speeds. The construction of these apparatuses is
designed in such a way that all of the material present in the
container is continually in motion and each particle comes into
recurrent contact with a rotor. The rotors may, for example, have
the form of propellers, impellers or serrated wheels and the like.
Apparatus of this kind is available, for example, from Diosna,
Drais or Henschel, and the latest models achieve tangential speeds
of up to about 40 m/s.
[0043] Preference is given to the use of a high-speed or heating
mixer in which the tangential speed is from 15 to 40 m/s and the
ratio of inorganic salt to crude pigment is from 1:1 to 1:12. A
tangential speed of at least 30 m/s is particularly efficient.
A-tangential speed of above 40 up to about 60 m/s is entirely
desirable for the practice of the invention but is unfortunately
realizable only at great expense in terms of apparatus. A
rotational speed of from 20 to 30 m/s is particularly economic, a
ratio of inorganic salt to crude pigment used of from 1:4 to 1:8 is
particularly preferred.
[0044] It has also been found that using relatively larger
equipment not only enables a larger. throughput, but also gives
surprisingly better results. Thus, it is highly preferred to treat
from about 10 kg to about 1000 kg of pigment per batch. The use of
larger equipments (up to about 10'000 kg) would of course also be
preferred, as well as the use of continuously working equipment
(provided its design is such that the minimum dwell time of any
pigment particle is long enough for the desired result to be
obtained). Such apparatuses, however, require high investment
costs.
[0045] The treatment time depends on the overall amount of
substance, the rotational speed, and the cooling. In general, the
treatment time is from 1 minute to 72 hours, preferably from 10
minutes to 5 hours, with particular preference from 30 minutes to 2
hours. The temperature rises preferably to 100-200.degree. C., with
particular preference to 120-170.degree. C., most preferably from
130 to 160.degree. C.
[0046] As soon as new similar devices will appear which allow to
get tangential speeds over 40 m/s, we recommend the skilled artisan
to test them at all speeds from 30 m/s up to the maximal speed. We
expect that these devices will yield at least equivalent and
probably even better results, likely in a shorter time.
[0047] Further constituents should judiciously be avoided, and
impurities minimized. In particular, other than the pigment, there
should be essentially no other organic substances, especially no
solvents or polymers. The proportion of extraneous organic
substances is judiciously not more than 2% by weight, preferably
not more than about 5% by weight, based on the crude pigment
used.
[0048] Suitable inorganic salts are those described later on below.
It has been found that surprisingly better results are obtained if
a relatively coarse inorganic salt is used, preferably a salt
having an average particle size (maximum of the particle size
distribution) of from 200 .mu.m to 1 mm.
[0049] The process is particularly suitable for organic pigments of
the quinacridone, anthraquinone, perylene, indigo, quinophthalone,
indanthrone, isoindolinone, isoindoline, dioxazine, azo,
phthalocyanine or diketopyrrolopyrrole series, examples being
Colour Index Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12,
Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 15, Pigment
Yellow 62, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 83,
Pigment Yellow 93, Pigment Yellow 95, Pigment Yellow 109, Pigment
Yellow 110, Pigment Yellow 111, Pigment Yellow 120, Pigment Yellow
128, Pigment Yellow 129, Pigment Yellow 139, Pigment Yellow 147,
Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 168, Pigment
Yellow 174, Pigment Yellow 175, Pigment Yellow 180, Pigment Yellow
181, Pigment Yellow 185, Pigment Yellow 188, Pigment Yellow 191:1,
Pigment Yellow 194, Pigment Yellow 199, Pigment Orange 5, Pigment
Orange 13, Pigment Orange 16, Pigment Orange 22, Pigment Orange 31,
Pigment Orange 34, Pigment Orange 48, Pigment Orange 49, Pigment
Orange 61, Pigment Orange 64, Pigment Orange 71, Pigment Orange 73,
Pigment Red 2, Pigment Red 4, Pigment Red 5, Pigment Red 23,
Pigment Red 42, Pigment Red 48:1, Pigment Red 48:2, Pigment Red
48:3, Pigment Red 48:4, Pigment Red 52:2, Pigment Red 53:1, Pigment
Red 57:1, Pigment Red 112, Pigment Red 122, Pigment Red 144,
Pigment Red 146, Pigment Red 166, Pigment Red 177, Pigment Red 184,
Pigment Red 185, Pigment Red 202, Pigment Red 206, Pigment Red 214,
Pigment Red 209, Pigment Red 220, Pigment Red 221, Pigment Red 222,
Pigment Red 242, Pigment Red 248, Pigment Red 254, Pigment Red 255,
Pigment Red 262, Pigment Red 264, Pigment Red 270, Pigment Red 272,
Pigment Brown 23, Pigment Brown 25, Pigment Brown 41, Pigment Brown
42, Pigment Green 7, Pigment Green 36, Pigment Blue 15:1, Pigment
Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:6, Pigment Blue 16,
Pigment Blue 25, Pigment Blue 26, Pigment Blue 29, Pigment Blue 60,
Pigment Blue 64, Pigment Blue 66, Pigment Violet 19, Pigment Violet
23, Pigment Violet 29, Pigment Violet 31, Pigment Violet 32,
Pigment Violet 37,
3,6-di(4'-cyanophenyl)-2,5-dihydropyrrolo[3,4-c]-p-
yrrole-1,4-dione or
3-phenyl-6-(4'-tert-butylphenyl)-2,5-dihydropyrrolo[3,-
4-c]pyrrole-1,4-dione.
[0050] Preferred pigment classes are quinacridones, anthraquinones,
isoindolinones, dioxazines, phthalocyanines and
diketopyrrolopyrroles, especially dioxazines, phthalocyanines and
diketopyrrolopyrroles, most preferred dioxazines and
diketopyrrolopyrroles. The most preferred anthraquinones are
indanthrones, the most preferred phthalocyanines are copper
phthalocyanines, and the most preferred azos are disazo
condensation pigments.
[0051] Independently from the pigment class, pigments are preferred
which contain at least 2 atoms of halogen in their molecule.
Preferably, from 1 to 4 of these halogen atoms are bond to phenyl
rings, most preferred 1 or 2, especially 1 atom of halogen per
chlorinated phenyl group. The maximal amount of halogenated atoms
depends on the number of phenyl rings available for substitution,
which is for example 8 in Pigment Yellow 110 or 16 in entirely
halogenated copper phthalocyanine having 4 phenyl rings. Suitable
halogens are fluorine, bromine or chlorine, preferably bromine and
chlorine, most preferred chlorine.
[0052] It is not known why the instant process leads to such
improvements of halogenated and in particular chlorinated pigments.
However, we suspect that this may be due to the their unique
physical characteristics and crystal lattices, which also lead for
example to extremely low solubility and good weather fastness.
[0053] Most preferred are pigments having a total of 2 chlorine
atoms in their molecule, of which many are listed above, such as in
particular Pigment Yellow 95, Pigment Red 202, Pigment Red 254,
Pigment Blue 64 and Pigment Violet 23. Some Pigment Green 36 also
have just 2 chlorine atoms. Especially preferred are Pigment Red
254 and Pigment Violet 23.
[0054] Inorganic pigments may likewise be treated by the same
process, examples being Pigment Yellow 53, Pigment Yellow 119,
Pigment Yellow 134, Pigment Yellow 164, Pigment Yellow 184, Pigment
Red 101, Pigment Red 104, Pigment Brown 24, Pigment Brown 33,
Pigment Blue 28, Pigment Blue 36, Pigment Green 17, Pigment Green
26, Pigment Green 50, Pigment Black 12, Pigment Black 27 or Pigment
Black 30.
[0055] The crude product of the formula (I) is known per se and is
also available commercially, for example as "Sumitone.RTM. Fast
Violet RL 4R base". The processes for preparing the other pigments
are all known and generally lead to crude pigments which are highly
suitable for amorphization. The initial crystal form is of minor
importance in the case of substantially complete amorphization.
[0056] In the case of the crude pigment, preference is given to a
coarsely particulate form, examples being crystallizates or
agglomerates having a length of 0.5 .mu.m or more for 50% by weight
of all of the individual particles observable under the optical
microscope. The particle size of the substantially amorphous,
finely particulate product is preferably below 0.3 .mu.m for 80% by
weight of all particles in the product.
[0057] The substantially amorphous, fine-particled pigment form
prepared in this way may be isolated, and used as a colorant, by
customary, known processes. It may also be recrystallized in usual
manner in a high boiling, inert polar solvent. However, it has
proved particularly advantageous to subject products pretreated in
this way, without separating off the inorganic salt, to salt
kneading in the presence of a solvent. Completely surprisingly,
pigments are obtained in this case which have considerably better
properties than by amorphization with subsequent frictionless
recrystallization or by kneading alone.
[0058] Accordingly, the invention further provides a process for
preparing a pigment as disclosed above, which comprises
[0059] subjecting a crude pigment or mixture of crude pigments and
a crystalline inorganic salt or mixture of crystalline inorganic
salts together, essentially in the absence of other constituents,
to the action of a rotor having a tangential speed of at least 10
m/s, so that a temperature of at least 80.degree. C. is attained by
means of friction effects; and subsequently.
[0060] kneading the product of this treatment with an organic
liquid, during which it is possible if desired to add additional
substances selected from the group consisting of inorganic salts,
inert additives and colorants.
[0061] The inorganic salts and organic liquids described later on
below, and also mixtures thereof, are suitable. It is not necessary
to use in each case the same inorganic salt, or the same grade
thereof, for the amorphization and for the kneading. On the
contrary, it has surprisingly been found that it is advantageous to
use a coarser-particled salt for the amorphization than for the
kneading.
[0062] In the case of this kneading, it is preferred to employ the
abovementioned conditions and proportions of organic liquid to
inorganic salt and of organic liquid to the overall weight of
inorganic salt and crude pigment.
[0063] For the kneading, it is possible if desired to add inert
additives known to the skilled worker, examples being binders,
fillers, antifoams, dispersants and other additives, in any
desired, known amounts, which are dependent on the inert additive
and on the target effect and may range from 1 ppm up to the
five-fold amount, based on the weight of the crude pigment.
[0064] For the purpose of adjusting the shade, it is likewise
possible to add any desired known colorants, examples being organic
and inorganic white, black and coloured pigments, or
water-insoluble dyes, such as disperse dyes.
[0065] Additional colorants may in particular also be derivatives
of pigments, in particular the oxidized or reduced form thereof
such as for example quinacridonequinones or dihydroquinacridones,
or also derivatives thereof such as pigments substituted by polar
groups and long chains which are well-known as dispersants or
rheology improvers.
[0066] Additional colorants may likewise be added in any desired
amount, these amounts being dependent on the shade to be
established and being calculable by the skilled worker using known
means, for example colour calculation computer programs.
[0067] Additional colorants are added, if desired, judiciously in a
ratio of from 1:99 to 99:1, based on the weight of the crude
pigment. Preference is given to a ratio of from 1:99 to 50:50. With
special preference, however, no additional colorants are used at
all, or they are used in amounts below 1: 99, for example from
0.01:99.99 to 0.99:99.01, based on the weight of the crude pigment.
This leads to pigments having coloristic properties equivalent to
those of the pigments, but depending on which additional component
is used, their properties such as rheology or dispersibility may be
significantly improved.
[0068] Exceptionally in the case of the compound of the formula
(I), additional colorants are added, if desired, with particular
preference in the ratio of from 0:100 to 20:80, with very
particular preference from 0:100 to 10:90, based on the weight of
the crude pigment.
[0069] All additional substances can be added at any desired point
in time during kneading, including in particular all of them at the
beginning.
[0070] If rather than one amorphized organic compound a plurality
thereof, for example 2, 3, 4 or 5, are used, then the single
components can be amorphized together, or they can also be first
amorphized and then blended before kneading. Of course, the
finished instant products may also be used as components in further
blends with one another, or also with other colorants which may or
may not have been treated by any known method as described
below.
[0071] When mixtures of compounds known to be suitable for the
purpose are used--examples being quinacridones and
diketopyrrolopyrroles--, then solid solutions or mixed crystals,
depending on the pigment classes, identities and proportions of the
said compounds, are generally obtained in a particularly efficient
and at the same time economic way. But there are surprisingly also
some exceptions. Coloristically advantageous mixtures in which the
crystal phases coexist in the final product are the object of
co-pending application PCT/EP 00/02442; nevertheless, the instant
process can also advantageously be used for producing them. In this
case, too, the components may be amorphized individually or else
all together.
[0072] Althought it would also be suitable to use more than 5
pigments with absolutely equivalent results, in practice there are
no advantages to do so. Preferred mixtures have 2 to 4 components,
especially 2 or 3 components, most preferred 2 components.
[0073] When mixtures are used, then the amount of each further
component can be independently from each other any amount from
coloristically effective (often from about 0.001 part by weight,
preferably at least 0.01 part by weight, most preferred at least
0.1 part by weight) to 1 part by weight, per part by weight of the
first component.
[0074] In the kneading process of the invention, the majority of
pigment particles are not reduced in size, but in contrast, by
virtue of the shear forces between the salt crystals in the
presence of the organic liquid, are advantageously converted into
an excellently crystalline pigment form. The resultant pigment has
superior fastness properties and generally a specific surface area
of from 60 to 150 m.sup.2/g, preferably from 80 to 140 m.sup.2/g,
with particular preference from 90 to 120 m.sup.2/g. The specific
surface area may be determined, for example, using the BET method
with nitrogen.
[0075] If binders are added, then depending on the amount thereof
the specific surface area may fall to about half of the levels
mentioned above.
[0076] Judiciously, the crystalline inorganic salt is soluble in
the organic liquid at .ltoreq.100 mg/l at 20.degree. C., preferably
.ltoreq.10 mg/l at 20.degree. C., and with particular preference is
virtually insoluble at 20.degree. C.
[0077] The inorganic salt and the organic liquid are preferably
each soluble in water to the extent of at least 1.0 g/100 ml. The
inorganic salt used is preferably aluminium sulfate, sodium
sulfate, calcium chloride, potassium chloride or sodium chloride,
which may if desired contain water of crystallization; particular
preference is given to sodium sulfate, potassium chloride or sodium
chloride.
[0078] For the kneading it is preferred to use a salt having an
average particle size of from 5 to 200 .mu.m, with particular
preference a salt having an average particle size of from 10 to 50
.mu.m.
[0079] As organic liquid it is preferred to use a ketone, an ester,
an amide, a sulfone, sulfoxide, a nitro compound, or a mono-, bis-
or tris-hydroxy-C.sub.2-C.sub.12alkane compound which is
substituted by 1 or 2 oxo groups and on one or more hydroxyl groups
may be etherified with C.sub.1-C.sub.8alkyl or esterified with
C.sub.1-C.sub.8alkylcarbonyl, or a mixture thereof. With particular
preference, the ketone, ester, amide, sulfone, sulfoxide or nitro
compound is an aliphatic or cycloaliphatic compound.
[0080] Judiciously, the organic liquid is neutral per se, although
acidic or basic impurities in customary small amounts are not
disruptive. Illustrative examples, but in no way limiting to the
invention, of neutral organic liquids are triacetin,
dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl
methyl ketone, cyclohexanone, diacetone alcohol, butyl acetate,
nitromethane, dimethyl sulfoxide, and sulfolane. Very particular
preference is given to an amide, sulfone or sulfoxide, most
preferably an amide, for example dimethyl sulfoxide, sulfolane,
N-methylpyrrolidone, dimethylacetamide or, in particular,
dimethylformamide.
[0081] In the case of pigments from classes other than carbazole
violet, it is also possible if desired to use other organic
liquids, for example alcohols or glycols, provided that the pigment
to be treated in each case is sufficiently soluble therein so that
crystal growth takes place under the stated conditions. If this is
not the case or not sufficiently the case, then judiciously an
abovementioned solvent should be used whose molecule contains at
least one oxo group.
[0082] The temperature during kneading is preferably from 10 to
60.degree. C. The rotary speed should be established, taking into
account the cooling if necessary, in such a way that under uniform
shear the kneaded composition is moved homogeneously, and the
temperature does not rise above the temperature range according to
the invention. Instances of local overheating or mechanical
overloading should be avoided as far as possible. Outstanding
results are obtained, for example, in a kneader of 5 l capacity at
rotary speeds of from 50 to 150 rpm and kneading times of from 6 to
24 h, these figures being by no means limiting and it being
possible for the rotary speeds to be lower in larger apparatuses,
for example.
[0083] Preferably, after kneading, the inorganic salt and the
organic liquid are washed with water, especially demineralized
water. Drying is conducted preferably at from -20 to 250.degree.
C./10.sup.-1 to 10.sup.5 Pa, with particular preference from 25 to
100.degree.C./10.sup.2 to 10.sup.5 Pa or from 100 to 200.degree.
C./10.sup.4 to 10.sup.5 Pa, with very particular preference around
80.degree. C. /10.sup.4 Pa.
[0084] The pigments obtained in accordance with the invention are
notable in particular for high colour saturation and an
astoundingly high colour strength. They have very attractive shades
with excellent fastness properties, good transparency and good
gloss.
[0085] The pigment of the invention may be isolated and dried in
pure form, in which case it is readily dispersible thereafter in
plastics, paints and printing inks using, for example, a ball mill
or bead mill. As a moist presscake, it can also be used directly to
prepare pigment dispersions.
[0086] Dispersions of the pigments of the invention are ideally
suited in particular as concentrates for preparing printing inks
which have excellent applications properties, especially attractive
colouristics with high colour strength.
[0087] The invention therefore additionally provides a printing ink
for a printing ink concentrate comprising a pigment of the
invention.
[0088] If desired, in order to improve the applications properties,
customary additives such as binders may be added to the pigment of
the invention prior to or during its isolation. Since the presence
of additives, owing to incompatibilities,frequently results in a
restriction of the possible fields of application, it is preferred
to refrain from adding them. A very particular advantage which has
been found is that pigment isolated without additives is
outstandingly compatible with both aqueous and nonaqueous media, so
that surprisingly good applications results can be obtained in both
cases.
[0089] A printing ink is a liquid or pastelike dispersion which
comprises colorants, binders and, if desired, solvents and
additives. In a liquid printing ink, the binder and, if present,
the additives are normally in solution in the solvent. Customary
viscosities in the Brookfield viscometer are from 0.1 to 20 Pa.s
(No. 4 spindle, 10 rpm). Printing ink concentrates are compositions
from which printing inks can be obtained by dilution. Ingredients
and compositions of printing inks and printing ink concentrates are
familiar to the skilled worker.
[0090] In addition to the pigments of the invention, the pigment
formulations or pigment dispersions of the invention may include
further colorants as described in connection with the kneading.
[0091] The printing ink concentrates of the invention contain the
pigments of the invention judiciously in a concentration of from 1
to 75% by weight, preferably from 5 to 50% by weight, with
particular preference from 25 to 40% by weight, based on the
overall weight of the printing ink concentrate.
[0092] The invention therefore likewise provides a printing ink
concentrate comprising from 1 to 75% by weight, preferably from 5
to 50% by weight, with particular preference from 25 to 40% by
weight, based on the overall weight of the printing ink
concentrate, of a pigment of the invention which is in dispersion
in a binder solution.
[0093] The printing inks of the invention contain the pigments of
the invention judiciously in a concentration of from 0.01 to 40% by
weight, preferably from 1 to 25% by weight, with particular
preference from 5 to 10% by weight, based on the overall weight of
the printing ink, and may be used, for example, for gravure
printing, flexographic printing, screen printing, offset printing,
or continuous or dropwise inkjet printing on paper, board, metal,
wood, leather, plastic or textiles, or else in special applications
in accordance with formulations which are general knowledge, for
example in publishing, packaging or freight, in logistics, in
advertising, in security printing or else in the office sector for
ballpoint pens, felt-tip pens, fibre-tip pens, inking pads, ink
ribbons or inkjet printer cartridges.
[0094] The invention therefore likewise provides a printing ink
comprising from 0.01 to 40% by weight, preferably from 1 to 25% by
weight, with particular preference from 5 to 10% by weight, based
on the overall weight of the printing ink, of a pigment of the
invention which is in dispersion in a binder solution.
[0095] Preference is given to printing ink concentrates and
printing inks on an aqueous acrylate basis. This is a reference to
polymers or copolymers obtained by addition polymerization of at
least one monomer containing a group 4
[0096] which are in solution in water or a water-containing organic
solvent. Suitable organic solvents are water-miscible solvents
commonly used by the skilled worker, examples being alcohols, such
as methanol, ethanol or an isomer of propanol, butanol or pentanol,
ethylene glycol or its ethers, such as ethylene glycol methyl ether
or ethylene glycol ethyl ether, or ketones, such as acetone, ethyl
methyl ketone or cyclohexanone. Preference is given to water and
alcohols.
[0097] The invention therefore also provides a printing ink
concentrate or printing ink of the invention wherein the binder
primarily comprises an acrylate polymer or copolymer and the
solvent is selected from the group consisting of water,
C.sub.1-C.sub.5alcohols, ethylene glycol,
2-(C.sub.1-C.sub.5alkoxy)ethanol, acetone, ethyl methyl ketone and
any mixtures thereof.
[0098] In addition to the binder, the printing ink concentrates and
printing inks of the invention may, if desired, also include
additives known to the skilled worker, in customary
concentrations.
[0099] For gravure or flexographic printing it is usual to dilute a
printing ink concentrate in order to prepare a printing ink which
may then be used in accordance with methods known per se.
Concentrates comprising the pigment compositions of the invention
are particularly suitable in this case.
[0100] The pigments of the invention are further also suitable for
preparing solid toners, wax transfer ribbons or very especially
colour filters.
[0101] Thus, another object of the invention are also the organic
pigments obtained by the instant process and their use in colour
filters. Their coloristic value is surprisingly high due to a
narrow absorption band with unprecedented steep slope, and at the
same time they possess an excellent crystallinity combined with a
small particle size and a particularly narrow particle size
distribution. Advantageously, both big and extremely fine particles
are lacking almost completely. The products exhibit both an
excellent rheology making possible a high concentration in use and
also superior coloristic properties and excellent fastnesses,
including outstanding light fastness.
[0102] Hence, the invention also relates to a substantially
crystalline organic pigment of the quinacridone, anthraquinone,
perylene, indigo, quinophthalone, indanthrone, isoindolinone,
isoindoline, dioxazine, azo, phthalocyanine or diketopyrrolopyrrole
series consisting of particles of average size from 0.01 .mu.m to
0.12 .mu.m, preferably from 0.02 .mu.m to 0.10 .mu.m, most
preferred from 0.03 .mu.m to 0.06 .mu.m, characterized in that the
total quantity of particles of size greater than 0.12 .mu.m and
smaller than 0.01 .mu.m is from 0 to 8% by weight, preferably from
0 to 4% by weight, most preferred from 0 to 2% by weight, based on
the weight of particles of size from 0.01 .mu.m to 0.1 .mu.m, and
the full width at half maximum (FWHM) of the highest resolved peaks
on a CuK.sub.60 radiation X-ray powder diagram is from about 0 to
0.68 .degree.2.theta., preferably from 0.1 to 0.6 .degree.2.theta.,
most preferred from 0.2 to 0.5 .degree.2.theta., with particular
reference to about 0.425 .degree.2.theta..
[0103] In general, measuring solely the highest intensity resolved
peak should be deemed appropriate. The minimum peak width depends
on the instrument's resolution and can be determined by the
Debye-Scherrer formula. For determining the full width at half
maximum, it is only suitable to use an instrument the resolution of
which is high enough in order not to influence significantly the
peak width to be measured.
[0104] The invention also pertains to the use of the instant
pigments in colour filters, which can themselves be used for
example in electro-optical systems such as TV screens, liquid
crystal displays, charge coupled devices, plasma displays or
electroluminescent displays and the like. These may be, for
example, active (twisted nematic) or passive (supertwisted nematic)
ferroelectric displays or light-emitting diodes.
[0105] The pigments will generally be used in the manufacture of
colour filters as a dispersion in an organic solvent or water.
There are several ways to manufacture these colour filters, which
follow two mainstreams:
[0106] Direct patterning during applying;
[0107] Patterning after applying the pigment.
[0108] Direct patterning can be obtained by several printing
techniques, such as impact (off-set, flexography, stamping,
letterpress etc.) as well as non-impact (ink jet techniques).
[0109] Other direct patterning techniques are based on lamination
processes, electronic discharging processes like electro-deposition
and some special colour proofing methods, like the so-called
Chromalinm.TM. process (DuPont).
[0110] For impact printing techniques, the pigment may be dispersed
in water or organic solvents by standard de-agglomeration methods
(Skandex, Dynamill, Dispermat and the like) in the presence of a
dispersant and a polymeric binder to produce an ink. Any dispersion
technique known in the fuels, including the choice of solvent,
dispersant and binder, can be used. The type of ink and its
viscosity depend on the application technique and are well-known to
the skilled artisan. Most usual binders, to which the invention is
of course not limited, are (meth)acrylates, epoxies, PVA,
polyimids, Novolak systems and the like as well as combinations of
these polymers.
[0111] The ink dispersion then can be printed on all kind of
standard printing machines. Curing of the binder system is
preferably achieved by a heating process. The three colours can be
applied at once or in different printing steps with intermediate
drying and/or curing steps, for example one colour at the time in
three printing steps.
[0112] Inks for use in ink jet, for example piezo or bubble jet,
can be prepared likewise. They generally contain a pigment
dispersed in water and/or one or a mixture of many hydrophilic
organic solvents in combination with a dispersant and a binder.
[0113] For ink jet printing a standard ink jet printer can be used
or a dedicated printer can be built in order to optimize for
example the printing speed etc.
[0114] For lamination techniques, like thermal transfer and the
like, a web system has to be made: The pigment is dispersed in a
solvent or water with dispersant and binder and coated on a foil
and dried. The pigment/binder system can be patternwise or
uniformly transferred toga colour filter substrate with the help of
energy (UV, IR, heat, pressure etc.). Depending on the technique
used, the colourant for example may be transferred alone (dye
diffusion or sublimation transfer), or the colourant dispersion may
be entirely transferred including the binder (wax transfer).
[0115] For electrodeposition, the pigment has to be dispersed in
water together with an ionized polymer. By means of an electrical
current, the ionized polymer is deionized at the anode or the
cathode and, being insoluble then, deposited together with the
pigments. This can be done on patterned or patternwise shielded, by
a photoresist, (transparent) photo-conductors like ITO etc.
[0116] The Chromalin.TM. process makes use of a photosensitive
material, deposited on a colour filter substrate. The material
becomes tacky upon UV exposure. The so called `toner`, comprising a
mixture or compound of pigment and polymer, is distributed on the
substrate and sticks on the tacky parts. This process has to be
done three to four times for R,G,B and eventually black.
[0117] Patterning after applying is a method based mostly on the
known photoresist technology, wherein the pigment is dispersed in
the photoresist composition. Other methods are indirect patterning
with the help of a separate photoresist or lamination
techniques.
[0118] The pigment may be dispersed into photoresists by any
standard method such as described above for the printing processes.
The binder systems may also be identical. Further suitable
compositions are described for example in EP 654711, WO 98/45756 or
WO 98/45757.
[0119] Photoresists comprise a photoinitiator and a
poly-crosslinkable monomer (negative radical polymerization), a
material to crosslink the polymers itself (for example a photoacid
generator or the like) or a material to chemically change the
solubility of the polymer in certain developing media. This
process, however, can also be done with heat (for example using
thermal arrays or an NIR beam) instead of UV, in the case of some
polymers which undergo chemical changes during heating processes,
resulting in changes of solubility in the mentioned developing
media. A photoinitiator is then not needed.
[0120] The photosensitive or heat sensible material is coated on a
colour filter substrate, dried and UV(or heat) irradiated,
sometimes again baked (photoacid generators) and developed with a
developing medium (mostly a base). In this last step only the
non-exposed (negative systems) or only the exposed (positive
systems) parts are washed away, giving the wanted pattern. This
operation has to be repeated for all the colours used.
[0121] Photosensitive lamination techniques are using the same
principle, the only difference being the coating technique. A
photosensitive system is applied as described above, however on a
web instead of a colour filter substrate. The foil is placed on the
colour filter substrate and the photosensitive layer is transferred
with the help of heat and/or pressure.
[0122] Indirect processes, with the above mentioned polymeric
binders without a photosensitive component, make use of an extra
photoresist, coated on top of the pigmented resist. During the
patterning of the photoresist, the pigmented resist is patterned as
well. The photoresist has to be removed afterwards.
[0123] More details about the manufacture of colour filters can be
found in text books, reviews and other scientific articles. The
skilled artisan will associate the instant invention with the use
of any such known technique as well.
[0124] The colour filters of the invention contain the pigments of
the invention judiciously in a concentration of from 1 to 75% by
weight, preferably from 5 to 50% by weight, with particular
preference from 25 to 40% by weight, based on the overall weight of
the pigmented layer.
[0125] The invention therefore likewise provides a colour filter
comprising a transparent substrate and a layer comprising from 1 to
75% by weight, preferably from 5 to 50% by weight, with particular
preference from 25 to 40% by weight, based on the overall weight of
the layer, of a pigment of the invention dispersed in a high
molecular mass organic material. The substrate is preferably
essentially colourless (T.gtoreq.95% all over the visible range
from 400 to 700 nm).
[0126] The binder may be any high molecular mass organic material
as defined below, binder materials as described above being only
examples.
[0127] The instant printing inks or photoresists for making colour
filters contain the pigments of the invention judiciously in a
concentration of from 0.01 to 40% by weight, preferably from 1 to
25% by weight, with particular preference from 5 to 10% by weight,
based on the overall weight of the printing ink or photoresist.
[0128] The invention therefore likewise provides a composition for
making colour filters comprising from 0.01 to 40% by weight,
preferably from 1 to 25% by weight, with particular preference from
5 to 10% by weight, based on the overall weight of the composition,
of a pigment of the invention dispersed therein.
[0129] The preferences relative to pigments for use in colour
filters follow the same lines as indicated above. A very
particularly preferred pigment for use in colour filters is Pigment
Red 254. When micronized by the instant process, Pigment Red 254
shows a hitherto never seen absorption spectrum when dispersed in a
polymer film. The absorption maximum at about 552 nm is shifted to
about 560 nm and the slope down to 590 nm is much steeper (FIG. 4).
This is highly advantageous as it enables a desired, substantially
higher absorption of green light (emission wavelength about 585
nm).
[0130] Thus, the invention also pertains to a pigment of the
formula 5
[0131] characterized in that a 50% by weight dispersion thereof in
a methacrylic resin, applied as a film of thickness such that the
absorption maximum in the area from 400 to 700 nm has an intensity
of 1.0.+-.0.1, said absorption maximum occurs at a wavelength from
556 to 596 nm, preferably from 557 to 565 nm. The maximum slope (at
the inversion point) on the bathochromic side of the absorption
maximum reaches preferably at least 5% change in absorption per 1
nm change in wavelength, based on the absorption at the absorption
maximum, most preferably at least 5.5% A/1 nm.
[0132] This pigment also may additionally contain other colorants
of structure different from (II), for example such as disclosed
above. When such colorants are added, then of course the absorption
maximum is shifted. Most suitable additional colorants are other
1,4-diketo-pyrrolo[3,4c]-pyrrole pigments, preferably Pigment
Orange 71, Pigment Orange 73, Pigment Red 255, Pigment Red 264,
Pigment Red 270, Pigment Red 272,
3,6-di(4'-cyanophenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-- 1,4-dione
or 3-phenyl-6-(4'-tert-butylphenyl)-2,5-dihydro-pyrrolo[3,4-c]py-
rrole-1,4-dione. The additional components will shift the mixture's
spectrum hypsochromically or bathochromically depending on their
own hue or on the eventual formation of solid solutions or mixed
crystals. Though the absorption maximum is shifted, however, the
slope is still advantageously steep.
[0133] Thus, the application also pertains to a
1,4-diketopyrrolo[3,4c]-py- rrole pigment, characterized in that a
50% by weight dispersion thereof in a methacrylic resin, applied as
a film of thickness such that the absorption maximum in the area
from 400 to 700 nm has an intensity of 1.0.+-.0.1, the maximum
slope on the bathochromic side of the absorption maximum in the
range from 500 to 650 nm reaches at least 5% change in absorption
per 1 nm change in wavelength, based on the absorption at said
absorption maximum.
[0134] Suitably, the methacrylic resin is substantially colourless,
examples thereof which are known to the skilled artisan being
copolymers of aromatic methacrylates with methacrylic acid of M,
from 30'000 to 60'000. The film is most appropriately made by
spin-coating.
[0135] The pigments of the invention are finally also suitable for
colouring high molecular mass organic materials in the mass.
[0136] The high molecular mass organic material to be coloured in
accordance with the invention may be natural or synthetic in origin
and normally has a molecular weight in the range from 10.sup.3 to
10.sup.8 g/mol. The said material may, for example, comprise
natural resins or drying oils, rubber or casein, or modified
natural substances, such as chlorinated rubber, oil-modified alkyd
resins, viscose, cellulose ethers or esters, such as cellulose
acetate, cellulose propionate, cellulose acetobutyrate or
nitrocellulose, but especially fully synthetic organic polymers
(both thermosets and thermoplastics), as obtained by addition
polymerization, polycondensation or polyaddition, examples being
polyolefins such as polyethylene, polypropylene or polyisobutylene,
substituted polyolefins such as polymers of vinyl chloride, vinyl
acetate, styrene, acrylonitrile or acrylates and/or methacrylates
or butadiene, and also copolymers of the abovementioned monomers,
especially ABS or EVA.
[0137] From the series of the polyaddition resins and
polycondensation resins, mention may be made of the condensates of
formaldehyde with phenols, known as phenolic resins, and the
condensates of formaldehyde with urea, thiourea and melamine, known
as amino resins, the polyesters used as paint resins, and indeed
both saturated resins, such as alkyd resins, and unsaturated
resins, such as maleate resins, and also the linear polyesters and
polyamides, or silicones.
[0138] The high molecular mass compounds mentioned may be present
individually or in mixtures, as plastic masses or melts, which may
if desired be spun into fibres.
[0139] They may also be present in the form of their monomers or in
the polymerized state in dissolved form as film formers or binders
for coating materials or printing inks, such as linseed oil
varnish, nitrocellulose, alkyd resins, melamine resins,
urea-formaldehyde resins or acrylic resins. When used in coatings,
the instant pigments exhibit higher fastnesses than the chemically
identical pigments of similar mean particle size or of similar
surface area. However, their use in coatings is relatively limited
due to their high transparency (for example in metallic
finishes).
[0140] Pigmentation of the high molecular mass organic substances
with the pigments of the invention takes place, for example, by
mixing such a pigment, in the form if desired of masterbatches,
into these substrates using roll mills, mixers or milling
apparatus. In general, the pigmented material is subsequently
brought into the desired ultimate form by techniques known per se
such as calendering, compression moulding, extrusion, spreading,
casting or injection moulding. In order to produce nonrigid
mouldings or to reduce their brittleness it is often desirable to
incorporate what are known as plasticizers into the high molecular
mass compounds prior to their shaping. Examples of such
plasticizers which may be used are esters of phosphoric acid,
phthalic acid or sebacic acid. In the process of the invention, the
plasticizers may be incorporated before or after the incorporation
of the pigmentary colorant into the polymers. A further
possibility, in order to obtain different hues, is to add fillers
and/or other colouring constituents such as white, coloured or
black pigments, and also effect pigments, in the particular desired
amount to the high molecular mass organic materials in addition to
the pigment compositions.
[0141] For pigmenting coating materials and printing inks, the high
molecular mass organic materials and the pigments of the invention,
alone or together with additives such as fillers, other pigments,
siccatives or plasticizers, are finely dispersed or dissolved in,
generally, an organic and/or aqueous solvent or solvent mixture.
One possible procedure here is to disperse or dissolve the
individual components alone, or else two or more together, and only
then to combine all of the components.
[0142] A further embodiment therefore additionally provides
mass-coloured high molecular mass organic material comprising
[0143] (a) from 0.05 to 70% by weight, based on the sum of (a) and
(b), of a pigment of the invention, and
[0144] (b) from 99.95 to 30% by weight, based on the sum of (a) and
(b), of a high molecular mass organic material.
[0145] Said material comprises both a ready-to-use composition or
an article formed therefrom, and a masterbatch, in the form of
granules, for example. If desired, the high molecular mass organic
material coloured in accordance with the invention may also
comprise customary additives, for example stabilizers.
[0146] A further embodiment therefore additionally provides a
process for colouring high molecular mass organic material in the
mass, which comprises incorporating therein a pigment of the
invention, for example by mixing the high molecular mass organic
material with the pigment composition of the invention, optionally
in the form of a masterbatch, in a manner known per se and
processing this mixture.
[0147] The examples which follow illustrate the invention without
restricting its scope (unless specified otherwise, "%" always
relates to % by weight):
EXAMPLE A1
[0148] Commercial, crude carbazole violet is ground in accordance
with DE-1 225 598 until the X-ray powder diagram (CuK.sub..alpha.)
no longer shows any significant signals.
EXAMPLE A2
[0149] The procedure of Example A1 is repeated but using the
grinding method of Example 8 of U.S. Pat. No. 4,785,999 until the
X-ray powder diagram no longer shows any significant signals.
EXAMPLE A3
[0150] The procedure of Example A1 is repeated but using the
grinding method of Example 1 of U.S. Pat. No. 5,194,088 and
extending the grinding duration until the X-ray powder diagram no
longer shows any significant signals.
EXAMPLE A4
[0151] The procedure of Example A1 is repeated but using the ball
mill method of the first part of Example III of U.S. Pat. No.
3,598,625 until the X-ray powder diagram no longer shows any
significant signals.
EXAMPLE A5
[0152] The procedure of Example A1 is repeated but using as
starting material the crude product from page 75 of the BIOS final
report 960, containing 25% salt from the synthesis.
EXAMPLE A6
[0153] The procedure of Example A2 is repeated but using as
starting material the crude product from page 75 of the BIOS final
report 960, containing 25% salt from the synthesis.
EXAMPLE A7
[0154] The procedure of Example A3 is repeated but using as
starting material the crude product from page 75 of the BIOS final
report 960, containing 25% salt from the synthesis.
EXAMPLE A8
[0155] The procedure of Example A4 is repeated but using as
starting material the crude product from page 75 of the BIOS final
report 960, containing 25% salt from the synthesis.
EXAMPLE A9
[0156] The procedure of Example A1 is repeated but using as
starting material the a product of JP-39/16786.
EXAMPLE A10
[0157] The procedure of Example A2 is repeated but using as
starting material the a product of JP-39/16786.
EXAMPLE A11
[0158] The procedure of Example A3 is repeated but using as
starting material the a product of JP-39/16786.
EXAMPLE A12
[0159] The procedure of Example A4 is repeated but using as
starting material the a product of JP-39/16786.
EXAMPLE A13
[0160] The procedure of Example Al is repeated but using as
starting material the a product of JP-52/935.
EXAMPLE A14
[0161] The procedure of Example A2 is repeated but using as
starting material the a product of JP-52/935.
EXAMPLE A15
[0162] The procedure of Example A3 is repeated but using as
starting material the a product of JP-52/935.
EXAMPLE A16
[0163] The procedure of Example A4 is repeated but using as
starting material the a product of JP-52/935.
EXAMPLE B1
[0164] A laboratory kneading apparatus with a capacity of 0.75 l is
charged with 50 g of amorphous dioxazine violet as per Example A1,
300 g of sodium chloride and 87 ml of dry dimethylformamide and the
speed of rotation is adjusted to 80 rpm. The walls of the kneading
apparatus are thermostatted at 45.degree. C. After 6 hours, the
speed of rotation is reduced to 5 rpm and the temperature is
allowed to fall to 20.degree. C., after which 120 ml of deionized
water are added slowly, the resulting mixture is discharged onto a
Buchner funnel and the solid product is washed with water until the
washing water is salt-free. The product is dried at 80.degree.
C./3.multidot.10.sup.3 Pa for 15 hours and sieved through a mesh of
size 0.4 mm.
EXAMPLES B2-B16
[0165] The procedure of Example B1 is repeated but using as
starting material the products of Examples A2-A16.
EXAMPLE C1
[0166] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 800 g of Sumitone.RTM. Fast Violet RL 4R base and 3200 g of
sodium chloride (Spezialsalz 100/95.TM., average particle size
approximately 70 .mu.m, Schweizer Salinen, Schweizerhalle,
Switzerland). Cooling is switched on and the rotary speed of the
triple propeller (diameter 220 mm) is adjusted to 3200 rpm. After
an hour, the internal temperature is 130.degree. C. The temperature
is then left to fall to 30.degree. C. at 50 rpm.
[0167] The powder is transferred to a laboratory kneading apparatus
with a capacity of 10 l (Werner & Pfleiderer, Germany). Then
1600 g of ground sodium chloride (particle size distribution with
maximum around 20 .mu.m) and 1400 ml of dimethylformamide are added
and the mixture is kneaded at 100 rpm for 8 hours. The walls of the
kneading apparatus are thermostatted at 45.degree. C.
[0168] The 2000 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLE C2
[0169] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 900 g of Sumitone.RTM. Fast Violet RL 4R base and 3600 g of
sodium chloride (Spezialsalz 100/95.TM., average particle size
approximately 70 .mu.m, Schweizer Salinen, Schweizerhalle,
Switzerland). Cooling is switched on and the rotary speed of the
triple propeller (diameter 220 mm) is adjusted to 3200 rpm. After
an hour, the internal temperature is 130.degree. C. The temperature
is then left to fall to 30.degree. C. at 50 rpm.
[0170] 250 g of this powder are transferred to a laboratory
kneading apparatus with a capacity of 0.75 1 (Werner &
Pfleiderer, Germany). Then 100 g of ground sodium chloride
(particle size distribution with maximum around 20 .mu.m) and 65 ml
of dimethylformamide are added and the mixture is kneaded at 80 rpm
for 6 hours. The walls of the kneading apparatus are thermostatted
at 40.degree. C.
[0171] Then 120 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLE C3
[0172] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 900 g of Sumitone.RTM. Fast Violet RL 4R base and 3600 g of
sodium chloride (particle size distribution with a maximum around
20 .mu.m). Cooling is switched on and the rotary speed of the
triple propeller (diameter 220 mm) is adjusted to 3200 rpm. After
an hour, the internal temperature is 110.degree. C. The temperature
is then left to fall to 30.degree. C. at 50 rpm.
[0173] 250 g of this powder are transferred to a laboratory
kneading apparatus with a capacity of 0.75 l (Werner &
Pfleiderer, Germany). Then 100 g of ground sodium chloride
(particle size distribution with maximum around 20 .mu.m) and 65 ml
of dimethylformamide are added and the mixture is kneaded at 80 rpm
for 6 hours. The walls of the kneading apparatus are thermostatted
at 40.degree. C.
[0174] Then 120 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLE C4
[0175] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 1000 g of Sumitone.RTM. Fast Violet RL 4R base and 4000 g of
sodium chloride (particle sizes between 5 .mu.m and 700 .mu.m).
Cooling is switched on and the rotary speed of the triple propeller
(diameter 220 mm) is adjusted to 3200 rpm. After an hour, the
internal temperature is 155.degree. C. The temperature is then left
to fall to 30.degree. C. at 50 rpm.
[0176] 250 g of this powder are transferred to a laboratory
kneading-apparatus with a capacity of 0.75 l (Werner &
Pfleiderer, Germany). Then 100 g of ground sodium chloride
(particle size distribution with maximum around 20 .mu.m) and 65 ml
of dimethylformamide are added and the mixture is kneaded at 80 rpm
for 6 hours. The walls of the kneading apparatus are thermostatted
at 40.degree. C.
[0177] Then 120 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLE C5
[0178] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 800 g of .RTM.Irgazin Yellow 3RLTN (Pigment Yellow 110) and
3200 g of sodium chloride (Spezialsalz 100/95.TM., average particle
size approximately 70 .mu.m, Schweizer Salinen, Schweizerhalle,
Switzerland). Cooling is switched on and the rotary speed of the
triple propeller (diameter 220 mm) is adjusted to 3200 rpm. After
40 minutes, the internal temperature is 135.degree. C. The
temperature is then left to fall to 30.degree. C. at 50 rpm.
[0179] 2350 g of this powder are transferred to a laboratory
kneading apparatus with a capacity of 5 l (Werner & Pfleiderer,
Germany). Then 940 g of ground sodium chloride (particle size
distribution with maximum around 20 .mu.m) and 900 ml of diacetone
alcohol are added and the mixture is kneaded at 80 rpm for 5 hours.
The walls of the kneading apparatus are thermostatted at 45.degree.
C.
[0180] Then 1000 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLE C6
[0181] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 600 g of .RTM.Cinquasia Magenta RT-265-D (Pigment Red 202),
200 g .RTM.Irgazin Yellow 3RLTN (Pigment Yellow 110) and 3200 g of
sodium chloride (Spezialsalz 100/95.TM., average particle size
approximately 70 .mu.m, Schweizer Salinen, Schweizerhalle,
Switzerland). Cooling is switched on and the rotary speed of the
triple propeller (diameter 220 mm) is adjusted to 3200 rpm. After
60 minutes, the internal temperature is 130.degree. C. The
temperature is then left to fall to 30.degree. C. at 50 rpm.
[0182] 2000 g of this powder are transferred to a laboratory
kneading apparatus with a capacity of 5 l (Werner & Pfleiderer,
Germany). Then 800 g of ground sodium chloride (particle size
distribution with maximum around 20 .mu.m) and 750 ml of diacetone
alcohol are added and the mixture is kneaded at 80 rpm for 5%2
hours. The walls of the kneading apparatus are thermostatted at
35.degree. C.
[0183] Then 1000 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLE C7
[0184] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 850 g of .RTM.Cromophthal Blue 4GLP (Pigment Blue 15:3) and
3400 g of sodium chloride (Spezialsalz 100/95.TM., average particle
size approximately 70 .mu.m, Schweizer Salinen, Schweizerhalle,
Switzerland). Cooling is switched on and the rotary speed of the
triple propeller (diameter 220 mm) is adjusted to 3200 rpm. After
one hour, the internal temperature is 130.degree. C. The
temperature is then left to fall to 30.degree. C. at 50 rpm.
[0185] 250 g of this powder are transferred to a laboratory
kneading apparatus with a capacity of 0.75 l (Werner &
Pfleiderer, Germany). Then 100 g of ground sodium chloride
(particle size distribution with maximum around 20 .mu.m) and 88 ml
of diacetone alcohol are added and the mixture is kneaded at 80 rpm
for 3 hours. The walls of the kneading apparatus are thermostatted
at 35.degree. C.
[0186] Then 120 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLE C8
[0187] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 500 g of .RTM.Irgazin DPP Red BO (Pigment Red 254), 500 g
.RTM.Cinquasia Magenta RT-265-D (Pigment Red 202), and 4000 g of
sodium chloride (particle sizes between 5 .mu.m and 700 .mu.m).
Cooling is switched on and the rotary speed of the triple propeller
(diameter 220 mm) is adjusted to 3200 rpm. After one hour, the
internal temperature is 135.degree. C. The temperature is then left
to fall to 30.degree. C. at 50 rpm.
[0188] 250 g of this powder are transferred to a laboratory
kneading apparatus with a capacity of 0.75 1 (Werner &
Pfleiderer, Germany). Then 100 g of ground sodium chloride
(particle size distribution with maximum around 20 .mu.m) and 85 ml
of diacetone alcohol are added and the mixture is kneaded at 60 rpm
for 6 hours. The walls of the kneading apparatus are thermostatted
at 40.degree. C.
[0189] Then 120 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLE C9
[0190] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 1000 g of .RTM.Irgazin DPP Red BO (Pigment Red 254) and 4000 g
of sodium chloride (Spezialsalz 100/95.TM., average particle size
approximately 70 .mu.m, Schweizer Salinen, Schweizerhalle,
Switzerland). Cooling is switched on and the rotary speed of the
triple propeller (diameter 220 mm) is adjusted to 3200 rpm. After
one hour, the internal temperature is 130.degree. C. The
temperature is then left to fall to 30.degree. C. at 50 rpm.
[0191] 300 g of this powder are transferred to a laboratory
kneading apparatus with a capacity of 0.75 l (Werner &
Pfleiderer, Germany). Then 120 g of ground sodium chloride
(particle size distribution with maximum around 20 .mu.m) and 90 ml
of diacetone alcohol are added and the mixture is kneaded at 100
rpm for 10 hours. The walls of the kneading apparatus are
thermostatted at 30.degree. C.
[0192] Then 120 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm. The mean particle
size is about 70-75 nm.
EXAMPLE C10
[0193] Example C9 is repeated, with the difference that Pigment Red
254 prepared according to example 6 of U.S. Pat. No. 4,579,949
(particle size about 0.2-0.5 .mu.m) is substituted for .RTM.Irgazin
DPP Red BO. The results are similar.
EXAMPLE C11
[0194] A 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged
with 1000 g of .RTM.Irgazin DPP Red BO (Pigment Red 254) and 4000 g
of sodium chloride (Spezialsalz 100/95.TM., average particle size
approximately 70 .mu.m, Schweizer Salinen, Schweizerhalle,
Switzerland). Cooling is switched on and the rotary speed of the
triple propeller (diameter 220 mm) is adjusted to 3200 rpm. After
one hour, the internal temperature is 130.degree. C. The
temperature is then left to fall to 30.degree. C. at 50 rpm.
[0195] 300 g of this powder are transferred to a laboratory
kneading apparatus with a capacity of 0.75 l (Werner &
Pfleiderer, Germany). Then 90 g of ground sodium chloride (particle
size distribution with maximum around 20 .mu.m) and 75 ml of
diacetone alcohol are added and the mixture is kneaded at 100 rpm
for 6 hours. The walls of the kneading apparatus are thermostatted
at 35.degree. C.
[0196] Then 120 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLE C12
[0197] A 920 l rapid mixer (type RD900/Diosna) is charged with 60
kg of .RTM.Irgazin DPP Red BO (Pigment Red 254) and 360 kg of
sodium chloride (Spezialsalz 100/95.TM., average particle size
approximately 70 .mu.m, Schweizer Salinen, Schweizerhalle,
Switzerland). Cooling is switched on and the rotary speed of the
spindle (6 knifes of diameter 800 mm) is adjusted to about 750 rpm
(the most suitable range is from 700 to 1000 rpm). After 31/2
hours, the mixture is discharged from the mixer and cooled down to
room temperature.
[0198] 2500 kg of this powder (collected from several runs) are
transferred to a twin-arms kneading apparatus with a capacity of
3000 l (type DMK/De Dietrich). Then 460 l of diacetone alcohol are
added and the mixture is kneaded for about 18 hours (about 1500
rpm). The walls of the kneading apparatus are cooled to
5-10.degree. C. in order to control the temperature of the mass to
about 30-40.degree. C.
[0199] After addition of water, the resulting mixture is discharged
onto a filter and the solid product is washed with water until the
filtrate is salt-free. The product is dried at 80.degree.
C./3.multidot.10.sup.3 Pa for 15 hours and sieved through a mesh of
size 0.8 mm. FIG. 1 is a TEM picture of this product.
EXAMPLE C13
[0200] 10 l mixer (FM 10 MB.TM., Henschel, Germany) is charged with
1000 g of .RTM.Cromophtal Yellow 3G (Pigment Yellow 93) and 4000 g
of sodium chloride (Spezialsalz 100/95.TM., average particle size
approximately 70 .mu.m, Schweizer Salinen, Schweizerhalle,
Switzerland). Cooling is switched on and the rotary speed of the
triple propeller (diameter 220 mm) is adjusted to 3200 rpm. After
one hour, the internal temperature is 130.degree. C. The
temperature is then left to fall to 30.degree. C. at 50 rpm.
[0201] 250 g of this powder are transferred to a laboratory
kneading apparatus with a capacity of 0.75 1 (Werner &
Pfleiderer, Germany). Then 100 g of ground sodium chloride
(particle size distribution with maximum around 20 .mu.m) and 110
ml of diacetone alcohol are added and the mixture is kneaded at 80
rpm for 6 hours. The walls of the kneading apparatus are
thermostatted at 40.degree. C.
[0202] Then 120 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
EXAMPLES C14-C26
[0203] Examples C1-C13 are repeated with the sole difference that,
based on the pigment weight, 10% of a solid, acetone-soluble resin
are added. The results are likewise excellent.
EXAMPLE C27
[0204] Pigment Red 254 is prepared according to example 1 of U.S.
Pat. No. 4,931,566. A very fine-sized pigment of particle size
<0.2 .mu.m is obtained.
EXAMPLE C28
[0205] A laboratory kneading apparatus with a capacity of 0.75 l
(Werner & Pfleiderer, Germany) is charged with 300 g of
fine-sized Pigment Red 254 prepared according to example C27 and
1200 g of ground sodium chloride (particle size distribution with
maximum around 20 .mu.m). 90 ml of diacetone alcohol are added and
the mixture is kneaded at 100 rpm for 10 hours. The walls of the
kneading apparatus are thermostatted at 30.degree. C.
[0206] Then 120 ml of deionized water are added, the resulting
mixture is discharged onto a Buchner funnel and the solid product
is washed with water until the washing water is salt-free. The
product is dried at 80.degree. C./3.multidot.10.sup.3 Pa for 15
hours and sieved through a mesh of size 0.8 mm.
[0207] The product obtained has a particle size of 0.06-0.10 .mu.m
and a relatively pure hue, but its crystallinity is inferior to
that of Example C10.
EXAMPLE C29
[0208] Example C28 is repeated, with the difference that
.RTM.Irgazin DPP Red BO (coarse particles, specific surface area
.about.15 g/m.sup.2) is substituted for the fine-sized product
according to example C27, and that sodium chloride of particle size
distribution with maximum around 50 .mu.m is used.
EXAMPLE D1
[0209] 210 g of SCX-8082.TM. (containing 30.0% dispersing polymer
Joncryl.RTM. 690, 2.15% ammonia and 67.85% water, 29.5% solids
content, S.C. Johnson Polymer) and 90 g of the product of Example
C1 are predispersed in a laboratory dissolver (Dispermat CV.TM.;
Hediger), at 6000 rpm for 15 minutes. The suspension is then
transferred to a 125 ml bead mill with dissolver attachment
(Dispermat SL.TM.; Hediger) charged with 207 g of zirconium
mixed-oxide beads of diameter 1.0 to 1.2 mm (Hermann Oeckel
Ingenieur GmbH, D-95100 Selb, Germany). The batch is then dispersed
at 4000 rpm for 10 minutes, the pump output being set at 60%,
corresponding to a time of 30 s for the first pass, and the
temperature, despite cooling, rises from 23.degree. C. to
38.degree. C.
[0210] A ready-to-use printing ink is obtained by diluting this
concentrate with a solution of 2565 g of Zinpol.RTM. 1519 (40%
strength all-acrylate solution in water/isopropanol, viscosity
2500-4000 mPa.s, Worlee-Chemie GmbH, D-21472 Lauenburg, Germany) in
2280 g of water and 855 g of isopropanol in a laboratory dissolver
at 6000 rpm and 23.degree. C. for 15 minutes. Printing is carried
out with this printing ink and a commercial gravure printing
machine (Rotova.TM., Rotocolor AG) onto standard HIFI kraft paper
(Zanders.TM. Mega Web 135gr No. 585585, Sihl & Eika Papier Ag,
CH-8800 Thalwil, Switzerland), the solids content after drying
being 0.860 g/m.sup.2. The result is a very brilliant and
transparent, violet print with excellent colour strength.
EXAMPLE D2-D17
[0211] The procedure of Example D1 is repeated using as starting
material the products of Examples B1-B16. The results are
comparable, colouristics, with L* values of from 46 to 47.5, C*
values of from 53 to 55 and h value 308, measured on an X-RITE
SP68.TM. reflection spectrometer (D.sub.10.degree..sup.65, 400-700
nm).
EXAMPLE D18 (COMPARATIVE)
[0212] The procedure of Example D1 is repeated but using as
starting material the product Hostaperm.RTM. Violet RL Special
(Clariant), which is known for particularly good colour strength
and saturation. The result is a violet print with the following
colour coordinates, measured on an X-RITE SP68.TM. reflection
spectrometer (D.sub.10.degree..sup.65, 400-700 nm): L*=48, C*=52,
h*=307.
EXAMPLE E1-E5
[0213] The crystallinity of the products according to examples C10,
C12, C27 and C28 as well as commercially available .RTM.Irgaphor
DPP Red B-CF (mean particle size .about.50 nm; Ciba Specialty
Chemicals Inc.) is compared using a Rigaku RAD2C X-ray
diffractometer (CuK.sub..alpha., 40 kV, 40 mA). The pigments are
filled up in a standard aluminium sample holder. The divergence
(DS) and scattering (SS) slits are adjusted to 0.5.degree., the
receiving slit (RS) to 0.15 mm. The diffracted x-ray beam is
monochromatised and measured by a scintillation counter.
2.theta.-.theta. scanning is done with the fixed time method
(.tau.=2 s with a step of 0.020) to minimize the effect of x-ray
statistic fluctuation. The corrected data are processed with
smoothing and background substraction using the Savitzky-Golay and
Sonnveld-Visser methods, respectively.
[0214] The peak width at half the intensity of the peak maximum is
measured for the main peak at about 28 .degree.2.theta.. The
results are as follows:
1 full width at half max- example pigment imum (.about.28 [.degree.
2 .theta.]) count/s E1 according to C10 0.612 757 E2 according to
C12 0.423 1028 E3 according to C27 0.826 1006 E4 according to C28
0.894 721 E5 .RTM. Irgaphor DPP Red B-CF 0.795 1093
[0215] The precision depends both on the peak width and on the
number of counts at the maximum, which itself depends on the peak
width, too. Thus, broader full widths at half maximum (in this case
above 0.70) are less precise.
[0216] FIG. 2 shows the X-ray diffraction spectrum of a product
obtained in very close analogy to examples C12 and E2.
[0217] FIG. 3 shows the X-ray diffraction spectrum of a product
obtained in very close analogy to examples C28 and E4.
EXAMPLE F1-F5
[0218] The following substances are introduced into a 37 ml screw
bottle: 200 mg of the products according to examples C10, C12, C27
and C28 as well as commercially available .RTM.Irgaphor DPP Red
B-CF; 8 mg Solsperse S22000 (Zeneca); 32 mg Solsperse S24000
(Zeneca); 200 mg of a copolymer of aromatic methacrylates with
methacrylic acid of M.sub.w from 30'000 to 60'000; 1760 mg
(1-methoxy-2-propyl)-acetate and 5000 mg zirconia beads of diameter
0.5 mm. The bottle is sealed with an inner cup then applied to a
paint conditioner for 3 hours to give a dispersion.
[0219] The dispersion thus obtained is cast onto a glass substrate
by means of spin coating, wherein a rotation speed is adjusted to
give a film having color coordination x=0.5500 (standard C light,
viewing angle 2.degree.), then dried at 60.degree. C. for 1 hour.
The optical properties of the dispersion films thus obtained are
measured by use of a UV/VIS spectrophotometer. The results are as
follows:
2 absorption maximum example pigment (VIS) film thickness F1
according to C10 558 nm 0.62 .mu.m F2 according to C12 560 nm 0.62
.mu.m F3 according to C27 554 nm 0.62 .mu.m F4 according to C28 557
nm 0.62 .mu.m F5 .RTM. Irgaphor DPP Red B-CF 553 nm 0.62 .mu.m
[0220] FIG. 4 shows the absorption spectra from 350 to 770 nm of
the colour filters according to examples F2 and F3. The maximum
slope (decrease in absorption) in the region from 570 to 580 nm is
6.16% A/nm around 579 nm for example F2 and 4.39% A/nm around 575
nm for example F3.
EXAMPLE G1
[0221] The dispersion film according to example F2 is heated to
270.degree. C. for 60 minutes in an oven at the air. Optical
microscope images of the films are taken after heat treatment. The
heat stability is much better than that of other pigment
dispersions suitable for red color filter applications.
EXAMPLE H1
[0222] 15 g of pigment and 15 g lithium stearate (metal soap, any
kinds) are mixed by homogenizer at 3000 rpm for 3 minutes. 1.2 g of
this dry mixture and 600 g of PET-G pellet (pigment concentration:
0.1%) are tumbled by 2-roll for 15 minutes in a glass bottle. The
obtained composition is then injection moulded to platelets at
260.degree. C. for 5 minutes. The CIE 1976 colour coordinates are:
L*=58.1 C*=35.3 h=3.7. The heat stability is high.
* * * * *