Note: Descriptions are shown in the official language in which they were submitted.
1 160~0~
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3-12916/~
Process for the preparation of pigment alloys
It is known that so-called super alloys, which are
commercially available, are obtained by grinding together
various metal, metal oxide or metal carbide powders in
high-capacity ball mills (Scientific.~American 234/5, page
40 (1~76))
It is also known that, in the case o~ pigments
which are very closely related in terms of colour and
structure, mixed crystals can be produced by grinding or
reprecipitation ~rom sulfuric acid (see U.S. Patent
Specification 3,081,188 and German Offenlegungsschrift
2,842,468). :
Moreover, it is known that the mixing of pigments
which are very di~ferent from one another in terms of
colour and structure can lead to dull hues
German Auslegeschrift 27110,999 describes a pro-
cess for the preparation of Cu phthalocyanine pigments by
mixing Cu phthalocyanine with one or more tinting pigments,
a~ter which pigment mixtures are obtained byreprecipitation
in sul~uric acid, by boiling or by the dry-grinding o~ Cu
phthalocyanines with dioxazine compounds, isoindolinone
compounds, indolizinedione compounds, azo compounds or
thioindigo compounds, and these pigment mixtures are said
to give more intense blue colorations with redder tints.
It has been shown that pigment mixtures prepared
by the last-mentioned process bring certain advantages,
but are unsatisfactory in respect of clarity, dispersibi-
lity in plastîcs and t~.tiformity of the colorations.
;. ~
',
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It has now been found that, by subjecting a mixture
consisting of at least two pigments from different groups
of the perylene, phthalocyanine, perinone, quinacridone,
quinophthalone, isoindolinone, isoindoline, dioxazine,
anthraquinone, thioindigo, methine or azomethine series or
of the monoazo or disazo series of the 2,3-hydroxynaphthoic
acid arylide, acetoacetic acid arylide, pyrazolone or benz-
imidazolone group, to thorough wet-grinding in water until
the pigments are alloyed with one another on the microscopic
scale, pigment alloys are obtained which, in comparison
with conventional pigment mixtures have clearer colour
shades, better application properties and more favourable
physical properties.
In the case of pigments of the phthalocyanine,
methine or azomethine series, these can be both metal-free
pigments and metal complexes.
The pigments to be used as starting materials must
belong to two dif~erent pigment groups They must
differ in essential structural characteristics and not
only in the type o~ substituents or, in the case of metal
complexes, in the type of metal. Thus, it is possible
to start ~rom mixtures of one representative of the above-
mentioned series with another representative of this
series, for example a mixture o~ an isoindolinone with a
perylene or azo pigment, or a mixture of a phthalocyanine
with a dioxazine, azo, anthraquinone or perylene pigment,
or a mixture o~ a quinacridone with an indigoid or with
an azo, anthraquinone or dioxazine pigment. Particularly
good results are achieved by grinding pigments of similar
hardness, for example polycyclic pigments, such as
dioxazines, perylenes, isoindolinones, quinacridones and
phthalocyanines, with one another, or by grinding azo
pigments with azomethine pigments.
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The relative proportions of the pigments can vary
within wide limits. 0.1 to 50 parts by weight of the
pigment of one of the groups and 50-99.9 parts by weight
of at least one pigment of the other group are preferably
used per 100 parts by weight of a pigment mixture.
For the starting pigment mixture, the individual
components can be in medium-to-fine crystalline form, but
preferably in coarse- and medium-to-~ine crystalline form
or only coarse crystalline form.
To intensi~y the grindlng action~ it can be
advantageous to carry out the wet-grinding in the presence
of organic grinding aids which are subsequently to be
removed. Thus, for example, according to the process
described in German Offenlegungsschrift 1,209,852, the
aqueous wet-grinding can be carried out particularly
effectively in the presence of a substantially water-
insoluble organic compound which can subsequently be
removed by sublimation or steam dlstillation or extraction,
in particular solid hydrocarbons, such as naphthalene, or
j a chlorohydrocarbon, such as hexachloroethane or p-di-
¦ chlorobenzene, 0.5 - 1.5 parts o~ the grinding aid and 1 -
].2 parts of water advantageously being used per 1 part of
I dry pigment mixture.
Organic additives remaining in the product, such
1~0~2
4 --
as stearic acid, resinic acids, for example abietic acid
and hydrogenated abietic acid, resinic acid esters,
derivatives of a low-molecular or high-molecular addition
resin or polymerisation resin, waxes or polyethylene gly-
cols, can also be used as grinding aids, advantageously
in amounts of 0.01 to 0.30 part, but preferably in small
amounts, such as 0.01 to 0.15 part, of organic additive
per 1 part of dry pigment mixture. In this process,
such additives can additionally improve the application
properties of the pigment alloy.
For carrying out the process, the pigment mixture,
preferably suspended in the liquid together with the
organic grinding aid and/or organic additives, is intro-
duced into a wet-grinding device with a thorough action.
Any device which makes it possible to subject the
pigments and, if appropriate, the carrier to intense
mechanical forces, in a liquid medium, can be used as the
apparatus. A relatively large number of apparatuses of
this type are known. They are based, for example, on
the principle of a large velocity gradient produced in a
liquid medium, or a sudden change in direction, or, in
particular, on the effect of collision or the mutual
friction between grinding bodies, such as metal spheres,
glass spheres or porcelain spheres, plastic granules or;
particles of sand, which are set in motion by the rotation
of the vessel or, even more effectively, by vibrating
devices or stirrer-like devices, for example as in the
case of glass-bead mills.
The grinding temperature is not critical within
technically reasonable limits, but, in the case where
organic grinding aids are used, should be below their
melting point. The grinding is advantageously carried
out at temperatures between 5 and 80C, preferably at
room temperature. Changes in the pH value, for
example adjustment of pigment suspensions to an acid or
alkaline pH, can also bring advantages in certain cases.
The wet-grinding is continued until the pigments
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are alloyed with one another on the microscopic scale
This takes ~ hour to 24 hours, depending on the type of
mill, the composition of the pigment mixture and, if
appropriate, the grinding aid used. The time required
to achieve the optimum properties of the pigment alloy for
the special use envisaged can easily be determined by
those skilled in the art. When starting from coarse
crystalline pigments, the pigment crystals are greatly
comminuted by the thorough grinding. Depending on its
composition, the pigment alloy can be in a state similar
to that of a substance which is amorphous to X-rays,
Working-up is carried out in the customary manner
by separating off the grinding bodies and isolating the
pigment alloy by filtering the pigment suspension and dry-
ing the pigment, When using organic grinding aids
which are subsequently to be removed, these are advantage-
ously removed after the grinding bodies have been separated
off, for example by steam distillation of the pigment sus-
pension or by sublimation during the drying of~the pigment
press-cake.
The drying process is carried out in the conven-
tional manner, for example in a vacuum cabinet or circulat-
ing air cabinet, a paddle drier, a fluidised bed drier or
freeze drier or also a spray drier. ~uring the drying
of pigment press-cakes, irreversible agglomerations fre-
quently occur and this results in poor dispersibility.
Surprisingly, in comparison with the separately ground,
pure pigments, pigment alloys prepared according to the
invention undergo in most cases substantially less
irreversible agglomeration during drying, despite the
particles being very fine.
The pigment alloys obtained according to the
invention are sui-table for pigmenting high-molecular com-
pounds, for example cellulose ethers and cellulose esters,
such as ethylcellulose, acetylcellulose and nitrocellulose,
polyamides and polyurethanes or polyesters, natural resins
or synthetic resins, for example aminoplasts, especially
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urea/formaldehyde and melamine/formaldehyde resins,
alkyd resins, phenoplasts, polycarbonates, polyolefins,
such as polyethylene, polypropylene and polystyrene, poly-
vinyl chloride, polyacrylonitrile and polyacrylic acid
esters, thermoplastic or thermosetting acrylic resins,
rubber, casein, silicone and silicone resins, individually
or in mixtures. The high-molecular compounds mentioned
can be in the form of plastic masses or melts or in the
i~orm of spinning solutions, lacquers or printing inks.
Depending on the intended use, it proves advantageous to
use the pigment alloys as toners or in the form o~ pre-
parations.
Because of the possibility of producing speciaI
physical properties, the pigment alloys prepared according
to the invention can also be employed in other particular
fields of application. Examples are the use of pigment
alloy toners in the field of electrophotography, as
absorption pigments in solar cells or as catalysts for
diverse chemical reactions, for example redox reactions.
Pigment alloy toners with special properties, which can
also be used, for example, as electrical semi-c~onductors,
are advantageously obtained by the thorough grinding of
pigment mixtures containing a) pigments with electron-
donating properties and b) pigments with electron-accept-
ing prope~ties, or of pigments with electron-donating or
electron-accepting properties, together with organic addi-
tives with electron-donating or electron-accepting proper-
ties, respectively
To produce special forms of pigment, the pigment
alloy, suspended in water, and/or in organic solvents, can
also be subjected to an after-treatment, preferably under
the action of heat and/or, i~ appropriate, at a modified
pressure.
In contrast to the conventional pigment mixtures,
the pigment alloys obtained according to the invention are
distinguished by more favourable physical properties and
application properties, especially clearer and more uni-
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~orm hues, higher tinctorial strength and transparency andhigher gloss, and better dispersibility in plastics and
lacquers. Because demixing cannot take place, in con-
trast to the conventional mixtures, the hue is guaranteed
to renain constant. Compared with individual pigments,
the pigment alloys have a substantially smaller crystal
growth in organic solvents and, in many cases, an
improved fastness to light, weathering fastness and heat
resistance.
In addition, itis tobe particularlyemphasised that
theprocess accordingto theinvention isvery economical; novel
pigments with particular desired colour shades can be
prepared in a simple manner from commercial pigments.
In the following examples, parts and percentages
are by weight, unless stated otherwise, and the tempera-
tures are given in degrees centigrade,
Example 1:
a) 28 parts of the orange-coloured pigment (I) of the
formula
ca3 ~
C!~ , N N ~ Cl
Cl ~0 H~ ,
7 parts of perylenetetracarboxylic dianhydride (II) and ~
35 parts of finely divided hexachloroethane are suspended
in 630 parts~of water in a glass-bead mill with a capacity
of 2,000 parts by volume, and thoroughly ground, for 24
hours, with 1,900 parts of glass spheres (diameter:
~.5-5.0 mm), at a stirring speed of 320 rpm, with external
water-cooling The glass spheres are then separated
of~ from the suspension and subsequently washed to some
extent with water. In a stirred vessel, the hexa-
chloroethane is removed by means o~ steam distillation.
The pigment suspension is filtered at about 70 and the
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press-cake is washed with water, dried in a vacuum drying
cabinet at 70-80 and powdered. This gives 33 5 parts
of a pigment alloy (A) which can very readily be dispersed
in plasticised PVC and gives very intensely coloured,
clear, uniform, orange-red milled sheets with excellent
fastness properties~
b) The pigments I and II are ground separately, as
described in la), for 24 hours, with hexachloroethane as
the grinding aid, the glass spheres are separated off,
the hexachloroethane is removed by steam distillation and
the pigment suspensions are filtered. The press-cakes
of the separately ground pigments I and II, in the same
weight ratio as the powdered pigments above, are only
mixed well, by stirring them in water again without
further grinding, filtered off, washed and dried, afford-
ing a pigment mixture (B) which, compared with the pigment
alloy (A), has a substantially duller hue when incorporated
into lacquers and plastics and has distinctly visible
streaks of red perylene pigment when used to colour
plasticised PVC milled sheets.
c) Investigation of the recrystallisation behaviour:
1 part of each of the two pigment samples A and B
is stirred separately in 30 parts of o-dichlorobenzene for
44 hours at 150 - 160. At certain intervals of time,
samples are withdrawn and the increase in size of the
crystals is observed under a light microscope. In the
case of pigment mixture B, the perylenetetracarboxylic
dianhydride shows a constantly progressing, strong crystal
growth as a function of time, whereas in the case of pig-
ment alloy A, a very small crystal gro~th could be
observed, which ceased after 1 to 3 hours.
29,4 parts of C I, Pigment Yellow llO (iso-
indolinone) and 5.6 parts of perylenetetracarboxylic acid
diimide are ground together with 35 parts of finely
divided hexachloroethane, according to the process des-
cribed in Example la), and the mixture is worked up.
~his gives 33.8 parts of a brown pigment alloy which, when
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used for colouring plas-ticised PVC milled shee-ts, gives
brown, transparen-t, clear, uniform and intense colora-
tions with excellent fastness proper-ties The dis-
persibility of the pigment alloy is excellent. This
is surprising because the perylenetetracarboxylic acid
diimide pigment in the pure state is exceptionally poorly
dispersible in plastics. The pigment alloy addition-
ally exhibits equal dispersibility a~ lo~ as at high
shear strength. Wen used for colouring
lacquers, it exhibits very good fastness properties and
high gloss.
Example 3: 30 8 parts of C I. Pigment Yellow I10 and
4 2 parts of perylenetetracarboxylic acid diimide,
toge-ther with 3.9 parts of finely divided hydrogenated
abietic acid (Staybelite Resin ~ from Hercules), are
thoroughly ground, for 9 hours, in 670 parts bf water, in
a glass~bead mill with a capacity of 2,000 parts by volume,
with 1,900 parts of glass spheres (diameter: 4.5 - 5.0 mm),
at a stirring speed of abou-t 320 rpm, with external oold
water-cooling. The glass spheres are separated from~
the pigment suspension and washed withalittlewater. The
pigment suspension is then filtered, the press-cake is
washed with water and dried at 70 - 80 in a vacuum dry- -
ing cabinet and the pigmen-t is powdered This gives
37.8 parts of a pigment alloy con-taining appro*imately
1~% of Staybelite resin, which can be used with excellent
dispersibility for colouring plasticised PVC and gives
brown, transparent, clear milledshee-ts ofuniform colour
intensity and with very good fastness proper-ties.
The sheets exhibit equal dispersibility at low as at
high shear strength.
Example 4: In a stirred vessel, 195 par-ts of C.I. Pig-
ment Yellow 110 and 5 parts of 2,9-dichloroquinacridone~
together wi-th 22 2 parts of finely divided hydrogenated
abietic acid, are stirred well, ~or one hour, in 900 parts
of wa-ter. The pigment suspension is diluted wi~h water
to a weight of 2,000 parts. In a KDL--type Dyno mill
I ~60402
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irom Willy A. Bachofen, Basel, provided with a steel
grinding con-tainer wi-th a capaci-ty of 600 par-ts by volume,
filled with 480 - 510 parts by volume of glass spheres
having a diameter of 1 mm, the pigment suspension is
thoroughly ground, for 90 minutes, at a stirring speed of
3~000 rpm and a pumping speed of 30 rpm.
The pigment suspension is separated from the
glass spheres, which are subsequently washed with 500
parts o~ water. The suspension is filtered, the press-
cake is washed with 1,000 par-ts of water and dried in a
vacuum drying cabinet at 70 - 80 and the pigment is
powdered in an Osterizer mixer. This gives 210 parts
of a pigment alloy containing about 10% of hydrogena-ted
abietic acid, which, compared with the conventionally
prepared, i,e. unground, mixture, gives substan-tially
clearer, more uniform and more intense reddish yellow
colorations when incorporated into plas-ticised PVC.
The pigment alloy exhibits an excellent dispersibility
and equal dispersi~ility at low as at high shear strength.
When it is used for colouring lacquers, colorations wi-th
high gloss and excellent fastness properties are obtained.
Example 5: The procedure described in Example 4 is
repeated, excep-t that 2.5 parts of C.I. Pigment Red 177
(anthraquinone derivative) are used in place of -the 2,9~
dichloroquinacridone, affording a reddish yellow pigmen-t ;
alloy with equally good properties.
Example 6: The procedure described in Example 4 is ~
repeated, except that 2.5 parts of 1,4,9,10--tetrachloro-
2,6-dimethoxy-triphendioxazine are used in place of the
2,9-dichloroquinacridone, affording a reddish yellow pig-
ment alloy with equally good properties.
Example 7: The procedure described in Example 4 is
repeated, excep-t tha-t 2 5 par-ts of 2,9-dimethylquin-
acridone are used in place of the 2,9-dichloroquin-
acridone, af~ording a reddish yellow pigmen-t alloy with
equally good proper-ties.
Example 8: The procedure described in Example 4 is
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repea-ted, except that polys-tyrene granules having a dia-
meter of 1 - 1.5 mm are used in place of glass spheres,
affording a reddish yellow pigment alloy with equally good
properties.
Example 9: In a glass-bead mill with a capacity of 500
parts by volume, 12 parts of C.I. Pigment Yellow 110, 3
parts of C.I. Pigmen-t Blue 15:3 (~-Cu phthalocyanine) and
1.7 parts of finely divi~ed hydrogenated abietic acid are
s-tirred well, for 30 minutes, in 130 parts of water.
400 pa~rts of glass spheres having a diameter of 3.5 -
4.0 mm are added to the pigment suspension and the pigment
mixture is ground together with the resin for 8 hours at
a stirring speed of 320 rpm and with external water-
cooling. The pigment suspension is separated off from
the glass spheres, which are subsequently washed with a
littlewater,and is then filtered. The press-cake is
washed with water an~ dried at 70-80 in a vacuum drying
cabinet This gives 15.6 parts of a green pigment
alloy containing about 10% of hydrogenated abietic acid,
which, when converted to a powder and used for colouring
plasticised PVC milled sheets, gives intense, clear,
transparent, uniform, bottle-green colorations with very
good fastness properties. The pigment alloy exhibits
an excellent dispersibility and equal dispersibility at
low as at high shear strength.
~ ompared with the mixture, prepared in the con-
ventional manner,withthe sameproportions of the pigments
ground individually in the same way, the pigment alloy
does no-t exhibit any blue streaks of the phthalocyanine
pigment in the PVC sheet.
Example 10: The procedure of Example 9 is repeated,
except that 13.5 parts of C.I. Pigment Yellow 110 are
used in place of 12 parts, and 1.5 par-ts of C.I. Pigmen-t
Blue 15:3, No 74,160, are used in place of 3 parts,
affording a pigmen-t alloy which, when used for colouring
plastics and lacquers, gives ligh-t green colorations with
equally good properties.
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Example 11. In a glass-bead mill, 4 5 parts of C I.
Pigment Brown 23 (disazopigment), 10.5 parts of C I
Pigment Yellow 110 and 1.7 parts of finely divided
hydrogena-ted abietic acid are initially ground well to-
gether, for 30 minutes, in 130 parts of water, at room
temperature 400 parts of glass spheres having a dia-
meter of 3.5 - 4.0 mm are then added to the pigment sus-
pension, and the pigment mixture is ground together with
the resin for 9 hours at a stirring speed of 320 r~m and
with external water-cooling, The ground pigment sus-
pension is separated from the glass spheres, which are
subsequently washed with water, and is then filtered.
The press-cake is washed with water and dried a-t 70 - 80
in a vacuum drying cabine-t. This gives 15.6 parts of
a brown pigment alloy containing about lO~o of hydrogena-ted
abietic acid, which, when converted to a powder and used
for colouring plas-ticised PVC milled sheets, gives intense,
clear, transparent, neutral brown colorations with
excellent fastness properties The pigment alloy
exhibits an excellent disPersibility and equal disper-
sibility at low as at high shear strength. Compared
with the mixture, prepared in the conventional manner,
withthe sameproportions of the individual pigments, the
pigment alloy no longer exhibits any brown streaks of the
~azo pigment in the PVC sheet.
Example 12- The procedure described in Example 11 is
repeated,except tha-t13.5 par-tsof s-tabilised~-Cuph-thalocyanine
pigment are used in place of 4.5 parts of C.I Pigment
Brown 23 (disazopigment), and 1.5 parts of perylenetetra-
carboxylic acid diimide are used in place of 10 5 parts
of C I. Pigment Yellow 110, affording a pigment alloy
which, when used for colouring plasticised PVC milled
sheets, gives very transparent, clear, very intense, uni-
formly reddish blue colora-tions with excellent fastness
properties, This is surprising becausewiththe same pig-
men-t propor-tions of pigment mix-tures prepared in the con-
ventional manner, non-uniform and dull colorations are
l 1604~2
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obtained as a result of the poor dispersibility of the
individual pigments.
Example 13: The procedure described in Example 11 is re-
peated,except that 12 parts of C.I.~gLent Brown 23 are used
in place of 4.5 parts, and 3.0 parts of C.I. Pigment Red
88, No. 73,312 (tetrachlorothioindigo), are used in place
of the C.I. Pigment Yellow 110, and the mixture is ground
for 90 minutes instead of 9 hours, affording a pigment
alloy which, when used for colouring plasticised PVC
milled sheets, gives intense, clear, uniformly reddish
brown colorations with very good fastness properties.
Compared with a pigment mixtureprepared withthe samepig-
ment proportions but in the conventional manner, the pig-
ment alloy has a better dispersibility and gives more
transparent, clearer and more intense colorations.
Example 14: In a glass-bead mill with a capacity of 500
parts by volume, 5.0 parts of C.I. Pigment Yellow 83
(d~azo pigment), 9.0 parts of C.I. Pigment Red 144 (disazo
pigment) and 1 part of C.I Pigment Blue 15:3, No. 74,160
(~-Cu phthalocyanine), together with 1.7 parts of finely
divided hydrogenated abietic acid, are initially stirred
well, for 30 minutes, in 130 parts of water. 400 parts
of glass spheres having a diameter of 3.5 - 4.0 mm are
then added to the pigment suspension, and the pigment
mixture is ground together with the added, finely divided
hydrogenated abietic acid, for 3 hours, at a stirring
speed of about 320 rpm and with external water-cooling.
The ground pigment suspension is separated off from the
glass spheres, which are subsequently washedtosome extent
withwater~andis thenfiltered. Thepress-cake issubsequently
washed with water and dried at 70 - 80 in a vacuum drying
cabinet. After conversion to a powder, 15.9 parts of
a brown pigment alloy containing about 10% of hydrogenated
abietic acid are obtained, which can satisfac'orily be
incorporated into DOP pastes In comparison with DOP
pastes into which the individual pigments have been mixed
separately, the LOP pastes coloured with the pigment alloy
-
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have, on application, substantially more intense, clearercolorations which, in particular, have a constant hue.
Exam~le~ In a glass-bead mill with a capacity of 500
parts by volume, 6 parts of the 1:2 zinc complex of the
isoindoline of the formula
cW ,/ ~,
~' ~ c l! 1
and 1.5 parts o~ -the yellow metal complex of the formula
,-~ ,N C;d, '' !
together with 7.5 parts of finely divided hexachloroethane,
are thoroughly ground for 24 hours in 130 parts of water,
with 400 parts of glass spheres having a diameter of 3.5~-
4.0 mm, at a stirring speed of 320 rpm and with external
water-cooling The glass spheres are separated off from
the suspension and subsequently washed to some extent with
water. In a stirred vessel, the hexachloroethane is
distilled off by passing steam into the suspension.
The pigment suspension is filtered at about 70 and the
press-cake is washed with water, dried in a vacuum drying
cabinet at 70 - 80 and powdered. This gives 6.5 parts
of a pigment alloy which, when used for colouring plasti-
cised PVC milled sheets, gives intense, clear, trans-
parent yellow colorations with substantially better fast-
ness properties than the pigment mixture prepared in the
conventionalmanner withthe samepigment proportions.
Example 16: The procedure described in Example 15 is re-
peated,except that7.~ parts of naphthaleneare usedin place
of 7.5 parts of hexachloroethane as the grinding aid,
which is separated off by sublimation during the drying of
the pigment press-cake instead o~ by steam distillation,
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a~fording a pigme~t alloy with equally good properties.
Exam~le 17: The procedure described in Example 15 is
repeated, except that 7.5 parts of p-dichlorobenzene are
used in place of 7.5 parts of hexachloroethane as the
grinding aid, which is separated off by sublimation during
the drying of the pigment press-cake instead o~ by steam
distillation, affording a pigment alloy with equall~ good
properties
Example 18: In a glass-bead mill with a capacity of 500
parts by volume, 8.0 parts of C.I. Pigment Yellow 83,
6.o parts of C.I. Pigment Red 144 and 1 part of C.I.
Pigment Blue 15:3, No. 74,160 are thoroughly ground
together for 90 minutes in 125 parts of water, with 400
parts of glass spheres having a diameter of 3.5 - 4.0 mm,
at a stirring speed of 320 rpm and with external water-
cooling. The ground pigment suspension is separated
off from the glass spheres, which are subsequently washed
to some extent with water, and is then filtered. The
press-cake is subsequently washed with water and dried at
70 - 80 in a vacuum drying cabinet and the dry material is
powdered. This gives 14 parts of a brown pigment alloy
which can satisfactorily be incorporated into DOP pastes.
In comparison with DOP pastes into which the indi~idual
pigments are mixed separately, the DOP pastes coloured
with the pigment alloy have, on application, substantially
more intense, clearer colorations which, in particular,
have a constant hue.
_l~! In a beaker with a capacity o~ 500 parts by
volume, 5 parts of C,I. Pigment Yellow 83, 9 parts of C.I
Pigment Red 14~ and l part of C.I. Pigment Blue 15:3, No.
74,160, are thoroughly ground for 4 hours in 85 parts of
water, with 150 parts by volume of sand (Ottawa sand with
a diameter of 2 - 3 mm), using a nylon disc stirrer, at a
stirring speed of 2,000 rpm, with external water-cooling.
The ground pigment suspension is separated off from the
sand, which is subsequently washed to some extent with
water, and is then filtered. The press-cake is sub-
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sequently washed with water and dried at 70 - 80 in a
vacuum drying cabinet and the dry material is powdered.
This gives 14.4 parts of a brown pigment alloy which,
when used for colouring plasticised PVC milled sheets,
gives very intense, uniform colorations with good fastness
properties. Compared with a mixture prepared in the
conventionalmanner withthe sa~ pigment proportions, the
pigment alloy gives, on application, more intense, clearer
and more uniform, brown colorations.
Example 20: The proce*ure of Example 11 is repeated,
except that 1.7 parts of finely divided stearic acid are
used in place of 1.7 parts of hydrogenated abietic acid,
affording 15.7 parts of a pigment alloy containing about
10~ of stearic acid and having equally good properties.
Example 2 _ In a glass-bead mill with a capacity of 500
parts by volume, 6 parts of the polyanthrimide pigment
Vat Black 9, listed in the third edition of the Color
Index, and 1.5 parts of the anthraquinone pigment prepared
in Example 138 of ~ritish Patent Specification 1,415,037,
by condensing 1 mol o~ 4,4~-dibromobenzophenone with 2 mols
of l-amino-4-p-nitrophenylaminoanthraquinone, together with
7.5 parts of finely divided hexachloroethane, are thoroughly
ground for 24 hours in 130 parts of water, with 400 parts
of glass spheres having a diameter of 3.5 - 4.0 mm, at a
stirring speed of 320 rpm and with external water-cooling,
The glass spheres are then separated off from the suspen-
sion and subsequently washed to some extent with water.
In a stirred vessel, the hexachloroethane is distilled off
by passing steam into the suspension. The pigment sus-
pension is filtered at about 70 and the press-cake is
washed with water, dried in a vacuum drying cabinet at
70-80 and powdered. This gives 6.5 parts of a black
pigment alloy which, in the manner described in U.S.
Patent Specification 4,191,566~can be used with excellent
results as a black toner for electrophotographic image
processes.
"~:
1 160~02
- 17 -
Example 22- In a glass-bead mill with a capacity of 500
parts by volume, 5.4 parts of 1,5,9,10-tetrachloro-2,~-
dimethoxytriphendioxazine and 2.1 parts o~ the ~-modifica-
tion of perylenetetracarboxylic acid N,N'-bis-(3,5-
dimethylphenyl)-imide, together with 7.5 parts of finely
divided hexachloroethane, are thoroughly ground for 24
hours in 130 parts of water, with 400 parts of glass
spheres having a diameter of 3.5-4.0 mm at a stirring
speed of 320 rpm and with external water-cooling. The
glass spheres are then separated off from the suspension
and subsequently washed to some extent with water. In
a stirred vessel, the hexachloroethane is distilled off
b~ passing steam into the suspension. The pigment sus-
pension is filtered at about 70 and the press-cake is
washed with water, dried in a vacuum drying cabinet at 70-
80 and powdered This gives 6.6 parts of a magenta-
coloured pigment alloy which, in the manner described in
U.S. Patent Specification 4,191,566, can be used with
excellent results as a magenta toner for electrophoto-
graphic image processes. Compared~with the pigment mix-
ture prepared in the conventional manner and consisting of
the 5.4 parts of dioxazine pigment and 2 1 parts of peryl-
ene pigment listed above, the pigment alloy prepared
according to the invention has a significantly higher
photoelectrophoretic sensitivity
ExampleZ3 In a glass-bead mill with a capacity of 500
parts by volume, 13.2 parts of coarse crystalline ~-Cu
phthalocyanine pigment and 1.8 parts of chloranil are
thoroughly ground together for 24 hours in 125 parts of
water, with 400 parts of glass spheres having a diameter
of 3 5 to 4.0 mm, at a stirring speed of 320 rpm and with
e~ternal water-cooling. The ground pigment suspension
is separated off from the glass spheres, which are sub-
sequently washed to some extent with water, and is then
filtered. The press-cake is subsequently washed wi-th
water and dried to constant weight at room temperature in
'
I 160~02
- 18 -
a desiccator over concentrated sulfuric acid, and the dry
material is powdered. This gives 14 parts of a blue
mixture (A), the semiconductor properties of which were
investigated by measuring the electrical resistance.
By way of comparison, the electrical resistance of
pure Cu phthalocyanine pigment (C), and also o~ a powder
mixture of the same percentage composition, (B), obtained
in the customary manner by mixing finely divided Cu
phthalocyanine pigment for 20 minutes with chloranil in a
Turbula mixer from Willy A. Bachofen, Basel, was measured.
The electrical resistances (~) measured on the
compressed powders gave the following result:
P*
alloy sample (A) 8,5.105
mixture (B) 4.4.108
Cu phthalocyanine pigment (C) 4.9.101
* specific electrical resistance: + 0.3r~.cm at 25C.
The specific resistance of the alloy sample (C) is
several powers of ten lower than that of the comparison
samples. By thorough grinding of the donor component
(Cu phthalocyanine) and the acceptor component (chloranil),
it was possible to prepare a charge-transfer compound with
semiconductor properties.
Example_24: In a glass-bead mill with a capacity of 500
parts by volume, 12 parts of coarse crystalline ~-Cu
phthalocyanine pigment, 3 parts of carbazoledioxazine
(C.I. Pigment Violet 23) and 1.7 parts of finely divided
hydrogenated abietic acid are initially stirred well for
30 minutes in 130 parts of water. 400 parts of glass
spheres having a diameter of 3.5 to 4.0 mm are then added
to the pigment suspension, and the pigment mixture is
ground together with the resin for 5 hours, at a stirring
speed of 320 rpm and with external water-cooling. The
pigment suspension is separated off from the glass
spheres, which are subsequently washedwith alittlewater,
~f~
~-
l 160~02
-- 19 --
and is then filtered. The press-cake is washed with
water and dried at 70-80 in a vacuum drying cabinet.
This gives 15.7 parts of a blue pigment alloy containing
about lGyo 0l hydrogenated abietic acid, which, when con-
verted to a powder and used for colouring lacquers and
plastics, gives intense, clear blue colorations. The
dispersibility in plasticised PVC milled sheets is
excellent
Example 25: The procedure described in Example 11 is
repeated, except that 7 5 parts of C.I, Pigment Brown 23
are used in place of 4.5 parts, and 7.5 parts of C.I. Pig-
ment Yellow 110 are used in place of 10.5 parts, af~ording
a pigment alloy which, when used for colouring unplasti-
cised PVC window profiles, gives neutral brown colorations
with excellent weathering fastness.
A mixture of 130 parts of steatite spheres
having a diameter of 8 mm, 47 5 parts of alkyd-melamine
stoving lacquer, consisting of 60 parts of Beckosol 27-
320 ~ , 60% in xylene ~Reichhold Chemie AG), 36 parts o~
Super-Beckamin 13-501 ~ s 50/o in a 1:1 mixture of xylene
and butanol (Reichhold Chemie AG), 2 parts of xylene and
2 parts of ethylene glycol monomethyl ether, and 2.5 parts
of the pigment alloy obtained according to Example 1 is
dispersed in a 200 ml glass flask with a twist-of~ stopper,
for 120 hours on a roller stand. After separating off
the steatite spheres, 2.4 parts of the full shade mixture
dispersed in t~is way and 6.o parts of titanium dioxide
(Kronos RN 59 ~ from Kronos Titan GmbH) are mixed with
24.0 parts of the above alkyd-melamine stoving lacquer and
the mixture is sprayed onto aluminium sheets and then
stoved for 30 minutes at 130. This gives orange-red
colorations with excellent ~astness properties.
ExamE~Le 27~.; A mixture of 1 0 part of the pigment alloy
obtained according to Example 4, 1.0 part of antioxidant
l 160402
_ 20 -
(IRGANOX 1010 ~ from CIBA-GEIGY AG) and 1,000.0 part
high-density polyethylene granula~ ~estolen A 60-16 ~
from H~ls) is premixed for 15 minutes in a glass flask on
a roller stand. The mixture is then extruded in two
passes on a single-screw extrud~r and converted to granules,
the granules thus obtained are moulded on an Allround
Aarburg 200 injection-mouiding machine, at 220, to form
plaques, and the plaques are subsequently compression-
moulded for 5 minutes at 180. The moulded plaques
have intense reddish yellow hues with excellent fastness
properties.
Example 28: 2.0 parts of a 50% pigment preparation con-
sisting o~ 1.0 part of -the pigment alloy obtained accord-
ing to Example 4 and 1.0 part of Mg behenateareused in
place of 1.0 part of t~e pure pigment alloy, and the pro-
cedure is otherwise as described in Example 28, affording
reddish yellow moulded plaques with equally good proper-
ties.
Example 29: For colouring PVC, a mixture of 65 parts of
stabilised PVC, 35 parts of dioctyl phthalate and 0 2 part
of the pigment alloy obtained according to Example 12 is
prepared and worked between two rolls of a mill at about
150 for 5 minutes. The plasticised PVC sheet thus
obtained has a transparent, clear reddish blue coloration
with excellent fastness to light.
~$E~a~ A mixture of 92.0 parts of vinyl resin
Vinnol H65D~-J(from Wacker9 ~nich), 8.0 parts of vinyl
copolymer Vestolit HIS 7,~87 ~ ~rom HUELS), 1.5 parts of
plasticiser Reoplast 39 ~ (from CIBA-GEIGY AG), 1.4 parts
of stabiliser IRGASTAB BC-10 ~ (rom~CIBA-GEIGY AG), 1.4
parts of stabiliser IRGASTAB BC-29 ~ from CIBA-GElGY AG),
0.7 part of auxiliary stabiliser IRGASTAB CH-300 ~ ~rom
CIBA-GEIGY AG), 0.4 part of lubricant IRGAWAX 370 ~ (~rom
CIBA-GEIGY AG), 0.2 part of lubricant IRGAWA% 360 ~ ~rom
CIBA-GEIGY AG~ and 0.25 part of ligh~ stabiliser
TIN W IN 320 ~ ~rom CIBA-GEIGY AG) is prepared in a Fluid
mixer (from Papenmeier K.G., Detmold) by stirring for about
~`~`i
~ 160~02
21 -
5 minutes at a speed of 1,400 rpm.
1.5 parts of the unplasticised PVC mixture pre-
pared in this way and 0.075 part of the pigment alloy
prepared according to Example 11 are mixed in a Henschel
mixer (Henschelwerke G.M.B.H., Kassel) at a speed of about
2,000 rpm, at room temperature, ~or about 3 minutes.
The unplasticised PVC mixture pigm~nted in this
way is calendered on mixing rolls at 190 ~or 6 minutes,
at 25 rpm and with a speed ratio of 1:1.2, and compression-
moulded at 190 ~or 6 minutes on a B~rkle press, between
chrome-plated steel platens, to a layer thickness of about
1 mm. This gives a uniformly brown-coloured moulding
~hich has outstanding fastness to light and weathering
fastness.
`.~J
