Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1~73~80
The present invention relates to a process for the pre-
paration of easily dispersible phthalocyanine pigments of the
~-modification.
It is known that copper phthalocyanine (CuPc) of the ~-
modification which has been prepared by condensation according
to the phthalic acid anhydride process and, if desired, has
been extracted with dilute acid, can be brought into the pig-
ment form with the use of various methods of fine distribution.
Preferred methods of fine distribution are the grinding with
salt in the presence of additives preventing a phase trans-
formation or the grinding in organic solvents. The products
obtained according to these processes have sufficient tincto-
rial strength, however, their shade and the purity of the
! shade, and various technical properties must be improved. To
this effect, the crude pigment containing impurities must be
purified. The German Offenlegungsschriften Nos. 2,262,911 and
2,262,895 describe processes according to which the crude
; pigment is converted into the CuPc-sulfate with sulfuric acid
which dissolves the undesired impurities, the CuPc-sulfate is
separated, the pure sulfate is hydrolized and the pure CuPc
is isolated.
The pure CuPc of the ~-modification obtained upon that
purification is rearranged according to known methods, for ex-
ample by a thermal treatment or by the action of aromatic sol-
vents, into the ~-modification. When the highly pure CuPc of
the ~-modification obtained upon these purification and rearr-
- angement processes is finely distributed according to one of the
known mechanical processes, for example solvent grinding, pig-
ments are obtained unexpectedly that do not have any colori-
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1~738~
stical interest because of their dull shade and their extreme lack
of tinctorial strength.
The present invention is based on the discovery of a
process for the preparation of easily dispersible phthalocyanine pigments
of the ~-modification having high tinctorial strength and high stability
towards flocculation. According to the invention, there is provided
a process for the preparation of a copper phthalocyanine pigment of the
~-modification which comprises subjecting a highly pure copper phthalo-
cyanine of the ~-modification to a mechanical fine distribution together
with from 2% to 15% by weight, calculated on the copper phthalocyanine
of the ~-modification used, of a compound of the general formula
Pc - A (I)
in which Pc stands for a phthalocyanine radical, A stands for identical
or different groups selected from -COOM or -SO3M (where M is hydrogen,
an alkali metal, an ammonium ion, or one molar equivalent of an al-
kaline-earth metal, carbamoyl, sulfamoyl, N-alkylcarbamoyl of 1 to 12
carbon atoms, N-alkylsulfamoyl of 1 to 18 carbon atoms, N,N-dialkyl-
sulfamoyl with 1 to 4 carbon atoms in each alkyl, N-(2-aminoethyl)-
sulfamoyl, N-benzylsulfamoyl, N-(phenylethyl)-sulfamoyl, N-cyclohexyl-
sulfamoyl, N-alkyl-N-cyclohexylsulfamoyl with 1 to 4 carbon atoms in
the alkyl, N-phenylsulfamoyl, N-alkyl-N-phenylsulfamoyl with 1 to 4
carbon atoms in the alkyl, carboalkoxy with 1 to 4 carbon atoms in
the alkoxy, sulfonic acid phenyl ester, sulfonic acid alkyl ester
of 1 to 4 carbon atoms, and an aminomethyl group of the formula
-CH - N /
R2
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~738~0
in which Rl is hydrogen, alkyl of 1 to 18 carbon atoms, 2-aminoethyl, benzyl,
phenylethyl, phenyl, alkylphenyl ~ith 1 to 4 carbon atoms in the alkyl,
alkanoyl with 1 to 4 carbon atoms in the aIkyl moiety, or benzoyl, R2 is hy-
drogen or alkyl of 1 to 4 carbon atoms, or ~ and R2 together are phthaloyl;
m is 1 or 2 if A is -S03M, m is an integer of 1 to 4, if A is one of said
sulfamoyl or sulfonic acid ester groups, m is an integer of 1 to 3, if A is
a -COOM or, one of said carbamoyl or;carbalkoxy groups, or m is an integer of
1 to 6 (an integer of 2 to 4 is preferred), if A is said aminomethyl group.
The invention also provides a new copper phthalocyanine pigment of
the ~-modification obtained by the above defined process and characterized
by high tinctorial strength and by ready dispersibility and high stability to
flocculation in lacquer systems.
Preferred additives of the formula I are compounds in which A are
identical or different groups of the formula -COOH or -S03H and their alkali
metal, calcium, barium or ammonium salts, sulfamoyl, sulfonic acid phenyl
ester, N-alkylsulfamoyl of 1 to 18 carbon atoms, N~N-dialkylsulfamoyl with 1
to 4 carbon atoms in each alkyl, N-(2-aminoethyl)-sulfamoyl, N-benzylsulfamoyl,
N-(phenylethyl)-sulfamoyl, N-cyclohexylsulfamoyl, N-alkyl-N-cyclohexylsulfamoyl
with 1 to 4 carbon atoms in the alkyl, N-phenylsulfamoyl, N-alkyl-N-phenyl-
sulfamoyl with 1 to 4 carbon atoms in the alkyl, carbamoyl, or an aminoethyl
group of the for3ula
-CH - NHR , -CH - N / or -CH2 - N
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., '
- ` ' ' ',
~73~8V
in which Rl is alkyl of 1 to 18 carbon atoms, phenyl or alkylphenyl
with 1 to 4 carbon atoms in the alkyl, R3 and R4 are identical or
different alky~ each having 1 to 4 carbon atoms; m is 1 or 2, if
A stands for -COOH or -SO3H or their salts, or carbamoyl, m is 2
or 3, if A is one of said sulfamoyl or sulfonic acid ester groups,
and m is 2 to 4, if A is one of said aminomethyl groups.
Suitable phthalocyanines of the general formula I
are metal containing or metal free compounds, preferably copper
phthalocyanines which may carry further substituents in addition to
the substituents A, such as, for example copper phthalocyanine car-
boxylic acids, especially CuPc-monocarboxylic acid, -dicarboxylic
acid and mixtures thereof; alkali metal, alkaline earth metal or
aluminum salts of CuPc-carboxylic acids, salts of CuPc-carboxylic
acids with ammonia or aliphatic amines; copper phthalocyanine sul-
fonic acids and CuPc-sulfonic acid mixtures, especially copper
phthalocyanine-monosulfonic acid; alkali metal and alkaline earth
metal salts of copper phthalocyanine sulfonic acid, especially of
copperphthalocyanine monosulfonic acid; salts of CuPc-sulfonic acids
with ammonia or aliphatic amines; copper phthalocyanine carbon amides,
preferably those in which m is 1 to 2 which may be alkylated by alkyl
groups of 1 to 18 carbon atoms; copper phthalocyanine carboxylic acid
esters; copper phthalocyanine sulfonamides, preferably those in which
m is 2 to 3 which may be obtained by reacting CuPc-sulfochlorides with
primary or secondary aliphatic, cycloaliphatic, aromatic or mixed
aliphatic-aromatic amines, such as, for example am-
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.
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.
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1073880
monia, methyl amine, hexylamine~ ~-ethylhexyl amine, dodecyl amine, stearyl
amine, diethyl amine, di-n-butyl amine, cyclohexyl amine, ethylene diamine,
aniline, N-methyl aniline, benzyl amine, phenyl-ethyl amine; copper
phthalocyanine sulfonic acid esters, for example alkyl esters or aryl
esters; alkyl aminomethyl or dialkylaminomethyl copper phthalocyanines,
preferably those in which m is 2 to 4, which may be obtained by reacting
chloromethylated copper phthalocyanines with primary or secondary aliphatic
amines, such as, for example methyl amine, butyl amine, hexyl amine, octyl
amine, dodecyl amine, stearyl amine, di-n-butyl amine or ethylene diamine;
arylaminomethyl or alkylarylaminomethyl copper phthalocyanines, preferably
those in which m is 2 to 4 or phthalimidomethyl copper phthalocyanines,
preferably those in which m is 2 to 4 and which may be obtained by reacting
copper phthalocyanines with N-methylolphthalimide.
Except for other definitions, "alkyl" and "alkanoyl" are to be
understood as groups which contain from 1 to 4 carbon atoms in the alkane
radical, "aryl" is preferably "phenyl" and "cycloalkyl" are groups having
~¦ 4 to 8, preferably 6 carbon atoms.
`i By "highly pure copper phthalocyanine of the ~-modification", there
are to be understood products which were purified according to the methods
described in German Offenlegungsschriften Nos. 2,262,911 and 2,262,895 and
rearranged into the ~-modification according to known methods.
German Offenlegungsschrift No. 2,262,911 relates to a process for
the preparation of highly pure copper phthalocyanine pigments of the ~-
modification, which process comprises converting unsubstituted or substi-
; tuted, preferably halogenated, especially chlorinated (above all those
having a chlorine content of up to 6%) copper phthalocyanines having
different degrees of purity by means of suitable acids which dissolve
the impurities contained in the pigment, preferably sulfuric acid, into
- 6 -
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.
.
~73880
copper phthalocyanine salts capable of being isolated, separating them from
the acid, setting free from the copper phthalocyanine salts, under the
action of water, the copper phthalocyanines of the ~-modification in pure
form and subjecting the isolated copper phthalocyanines ;n an aqueous
suspension to a mechanical fine distribution. The starting material is
preferably dissolved in sulfuric acid or oleum and the solution diluted to
a concentration of acid of down to 80% by adding water or dilute sulfuric
acid or the crude material is introduced into sulfuric acid of 80 to 86%
strength.
German Offenlegungsschrift No. 2,262,895 relates to a process for the
purification of unsubstituted or substituted preferable halogenated,
especially chlorinated ~above all those having a chlorine content of up to
6% by weight) copper phthalocyanines which comprises introducing the copper
phthalocyanine into sulfuric acid of 84 to 88% strength or dissolving it at
first in concentrated sulfuric acid or oleum and then adjusting it with
water or dilute sulfuric acid to the concentration mentioned, subjecting
the copper phthalocyanine sulfate so formed at 60 - 100C, preferably 70 -
90C, in an inert gas atmosphere, preferably under nitrogen, to a process
of crystal growth, isolating the copper phthalocyanine sulfate and recover-
ing the copper phthalocyanine by the action of water. The sulfuric acid is
used preferably in 4 to 15 times the amount, calculated on the weight of
; the starting material, and the crystal growth process is preferably
carried out at a concentration of sulfuric acid of 85.5 to 86.5%.
The amount of compounds of the general formula I is in general within
the range of from 2 to 15%, calculated on the CuPc of the ~-modification used.
The amount required for obtaining optimum pigments depends on the
chemical constitution of the additive. ~hen CuPc-sulfonic acids are used,
the most favourable amount is within the range of ~ to 6%, in the case of the
-- 7 --
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1C~7388U
CuPc-carboxylic acids of 5 to 8%, and in the case of the other compounds of
the general formula I of 4 to 10%.
The preparation of an effective mixture of pure CuPc of the ~-
modification with an added compound of the general formula I is advantageous-
ly carried out by means of the process of fine distribution required for the
conditioning to the pigment, in which case the compounds of the general
formula I can be added at the beginning or during the process of the fine
distribution.
In principle, it is also possible to finely distribute the pure
CuPc of the ~-modification and compounds of the general formula I separately
and to mix the ground suspensions afterwards. The mixture of finely
distributed pure CuPc of the ~-phase and finely distributed additives of
the general formula I in the form of dry pigment powders, however, yields
pigments of less good properties.
When CuPc-carboxylic acids are used which are very important as
additives of the general formula I, an especially economical process for the
preparation of the mixture is the synthesis of CuPc containing the desired
amount of CuPc carboxylic acids by cosynthesis starting from phthalic acid
anhydride and a small amount of trimellitic acid or other suitable benzene-
polycarboxylic acids according to the phthalic acid anhydride process.
By following purification with sulfuric acid and rearrangement of
the phase, the products so synthesized yield the starting products required -
for the mechanical fine distribution. When other CuPc-derivatives of the
general formula I are used, that kind of cosynthesis is not expedient.
When CuPc-sulfonic acids are used as additive, a separate synthesis
is not necessary, as in the course of the purification of the CuPc by
reprecipitation from sulfuric acid the CuPc can partially be sulfonated.
The added CuPc-sulfonic acids and CuPc-carboxylic acids can be converted
-- 8 --
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,
73880
into the salts mentioned during or after the fine distribution by reacting
them with bases or with amines.
Suitable mechanical fine distribution processes are the generally
known ones, for example salt grinding in mills or kneaders, preferably the
grinding in a liquid grinding medium in a roller mill, a vibration mill, a
bead mill or a stirrer ball mill with the aid of the grinding bodies and
under the conditions generally used in practice.
Suitable grinding media are above all organic liquids and mixtures
of water with organic liquids. Water can be used only to a limited extent
because of the partial rearrangement of the phases into the a-phase. Suit-
able organic liquids are aliphatic and aromatic compounds. When aromatic
liquids are used, for example xylene, a prior rearrangement of phases of
the purified CuPc of the ~-phase can be dispensed with because the use of
.~:
such grinding media allows the rearrangement of phases into the ~-phase,
the mixture with an additive and the fine distribution to be carried out
in a single-step operation.
Preferred mixtures of water with organic liquids are homogenous
mixtures of water with primary, secondary or tertiary aliphatic aIcohols
having from 1 to 6 carbon atoms. Should coarser grains be required for
determined application fields, an after-treatment of the ground pigment
in organic or aqueous-organic media at elevated temperature may be advan-
tageous. The pigments are isolated according to known methods, preferably
by evaporation or spray-drying.
~; The pigment~ prepared according to ~he process of the invention are
suitable for dyeing lacquers, paper, plastics and synthetic resins,
synthetic fibers in the mass, for printing paper, textiles, films and sheets
and other materials and for metal effect lacquerings as well as paints.
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1~73880
The addition of the above-mentioned phthalocyanine derivatives of
the general formula I to phthalocyanines has been described in U.S. Patents
Nos. 2,526,345 and 3,028,392 and in German Patent No. 1,239,270. The
pigment mixtures described there;n show an improved stabilty towards
flocculation, however, they have a low tinctorial strength and a bad
dispersibility. In comparison thereto, the addition of these phthalo-
cyanine derivatives to highly pure phthalocyanines yields pigments having
a clear shade and a distinctly improved dispersibility and tinctorial
strength.
The following Examples illustrate the invention, the parts and
percentages being by weight.
E X A M P L E l:
For the preparation of copper phthalocyanine which contains about 8%
- calculated on the pure pigment - of copper phthalocyanine carboxylic acid,
1400 parts of nitrobenzene, 740 parts of phthalic acid anhydride, 21 parts
of trimellitic acid, 1170 parts of urea, 85 parts of ammonium chloride, 240
parts of anhydrous copper sulfate and 1 part of ammonium molybdate were
mixed and heated to 200C within 8 hours while stirring. The mixture was
after-stirred at 200C for 4 hours and after turning off the heating, 200
parts of nitrobenzene were added. The suspension was cooled to room
temperature, filtered and washed with nitrobenzene; the filter cake was
then washed with methanol and then with water. The moist filter cake was
introduced into a mixture of 2,000 parts of water and 1,000 parts of
~ concentrated hydrochloric acid, stirred at 90C for 5 hours, filtered and
; washed with water until neutral. The filter cake was dried at 100C. 716
Parts of a 93% crude copper-phthalocyanine were obtained that contained
about 8% - calculated on the pure dye - of copper phthalocyanine carboxylic
acid.
- 10 -
1~731~80
For the preparation of the pure dye, 21.5 parts of the crude dye
obtained were introduced in 215 parts of 86% sulfuric acid and the mixture
was stirred for 4 hours at 7Q - 80C in a nitrogen atmosphere. The mixture
was cooled to room temperature and the sulfuric acid concentration was
adjusted to 75% with 31.5 parts of water. The mixture of the sulfates of
copper phthalocyanine and copper phthalocyanine carboxylic acid was
filtered off, washed with 75% sulfuric acid and then hydrolized in 250 parts
of water. The dye was filtered off and washed until neutral. For the
rearrangement into the ~-modification, the moist filter cake was stirred
in 200 parts of water, 20 parts of chlorobenzene were added and the mixture
was stirred at 100C for 5 hours. The chlorobenzene was distilled off with
steam, the aqueous dye suspension was filtered and the filter cake was
dried at 100C.
20 Parts of pure copper phthalocyanine of the ~-modification were
obtained which contained about 8% of copper phthalocyanine carboxylic acid
being mainly in the form of the copper phthalocyanine monocarboxylic acid.
To bring it into the pigment form, the pure dye was ground with 120
parts of acetone and 1,200 parts of glass beads of a 2 mm diameter in a
porcelain mill for about 20 hours on a vibration table. Then, the pigment
was isolated and dried at 60C under reduced pressure. The pigment so
prepared serves for the dyeing of enamels according to known methods in
brilliant, greenish blue shades of high degree of purity and high color
intensity. As compared with known commercial dyestuffs, the pigment of
the invention is distinguished by a very good flocculation stability and
an excellent dispérsibility in lacquering systems.
When the fine distribution is effected with a mixture of 8.4 parts
of isobutanol and 111.4 parts of water or a mixture of 60 parts of iso-
propanol and 60 parts of water as grinding medium instead of 120 parts of
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1~73880
acetone, the pigments obtained already after a shorter grinding period have
the same quality.
E X A M P L E 2:
22.2 Parts of unsubstituted crude copper phthalocyanine ~in the form
of a 90% commercial product) were introduced into 200 parts of a 86%
sulfuric acid and stirred at 70C to 80DC for 4 hours in a nitrogen
atmosphere. The copper phthalocyanine sulfate obtained in the form of
coarse crystals was filtered off, washed with 80% sulfuric acid and -
hydrolized in 250 parts of water. Then, the dye was filtered off and
washed until neutral. The moist filter cake was introduced into 200 parts
of water to perform the rearrangement of the ~-modification into the ~-
modification, 20 parts of chlorobenzene were added and the mixture was
stirred at 100C for 5 hours. Then the chlorobenzene was eliminated by
steam distillation, the aqueous dyestuff suspension was filtered and the
filter cake was dried at 100C. 20 Parts of 100% pure copper phthalo-
cyanine of the ~-modification were obtained.
For the fine distribution, the pure dyestuff obtained and 1.2 parts
of copperphthalocyanine-4-carboxylic acid were ground with 120 parts of
acetone and 1,200 parts of glass beads of 2 mm diameter in a porcelain
mill for about 20 hours on the "Vibratom" vibration table. Then, the
pigment suspension was separated from the grinding bodies. The pigment
was isolated and dried at 60C under reduced pressure.
The pigment so obtained yields in the dyeing of enamels according
to known methods especially brilliant greenish blue shades of a high
tinctorial strength and a good stability towards flocculation. As compared
wi~h known commercial dyestuffs, the pigment of the invention is distin-
guished by a high degree of purity of the shade and an excellent dispersi-
bility in lacquering systems.
- 12 -
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1C~7388~
The pigment yields in polyvinyl chloride according to known methods
dyeings of high color intensity and a high degree of purity and good
dispersibility.
When instead of 120 parts of acetone 120 parts of methanol or 120
parts of isopropanol or 120 parts of glycolmonomethyl ether or 120 parts
of acetic acid-n-butyl ester were used as grinding medium, pigments of
equal quality were obtained. When the fine distribution is obtained not
by vibration grinding but by a continuous grinding in a bead mill, pigments
of equal quality were also obtained.
The fine distribution could also be performed with good success by
grinding on a roller mill.
E X A M P L E 3:
When the 1.2 parts of copper phthalocyanine monocarboxylic acid
indicated in Example 2 were replaced by 1.2 parts of copper phthalocyanine-
4,4'-dicarboxylic acid and the grinding and working up was performed as
described in Example 2, a pigment was obtàined which corresponded to the
pigment obtained in Example 2 with respect to its coloristal properties.
E X A M P L E 4:
When the 1.2 parts of copper phthalocyanine monocarboxylic acid
indicated in Example 2 were replaced by a mixture of 1 part of copper
phthalocyanine-4 carboxylic acid and 0.2 part of copper phthalocyanine-4-
carboxylic acid amide and the grinding and working up was carried out as
indicated in Example 2, a pigment was obtained which corresponded to that
indicated in Example 2 with respect to its coloristical properties.
E X A M P L E 5:
20 Parts of pure copper phthalocyanine of the ~-modification
(obtained according to the method described in Example 2) and 2 parts of
the sodium salt of copper phthalocyanine-4-carboxylic acid were ground
- 13 -
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.
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.
1(~7388~)
together with 120 parts of acetone and 1,200 parts of glass beads of 2 mm
diameter in a porcelain mill during about 20 hours on a "Vibratom"
vibration table. Then, the pigment suspension was separated from the
grinding bodies. The pigment ~as isolated and dried at 60C under reduced
pressure.
The pigment so obtained corresponded to that obtained according to
Example 2 with respect to its coloristical behaviour.
~hen instead of 2 parts of the sodium salt of copper phthalocyanine
monocarboxylic acid 2 parts of the barium salt of copper phthalocyanine
monocarboxylic acid were used as additive, a pigment was obtained which
had the same properties.
E X A M P L E 6:
32.6 Parts of unsubstituted crude CuPc (in the form of a 93%
commercial product) were introduced into 300 parts of a 86% sulfuric acid
and stirred at 70 to 80C for 4 hours in a nitrogen atmosphere. The so
obtained CuPc-sulfate in the form of coarse crystals was filtered off after
cooling to room temperature, washed with 80% sulfuric acid and then
hydrolized by introducing the filter cake into 300 parts of water. The
; copper phthalocyanine was filtered off and washed with water until neutral.
In order to attain the rearrangement of phases from the a-modification into
the ~-modification, the moist filter cake was introduced into 300 parts of
water, 30 parts of chlorobenzene were added and the mixture was boiled
` under reflux for 4 hours. Then, the chlorobenzene was removed by steam
; distillation.
The pigment suspension was filtered and the filter cake was dried at
100 C. 30 Parts of pure CuPc of the ~-modification were obtained.
For the fine distribution, the 30 parts of the pure CuPc so obtained
were ground after the addition of 1.2 parts of CuPc-monosulfonic acid
14
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1~7388~
(prepared by sulfonation of CuPc in oleum and having a sulfur content
of 5.1%) together with 150 parts of isopropanol and 1,200 parts of
glass beads of 2 mm diameter in a porcelain mill during 20 hours on
a "Vibratom" vibration table. Then, the pigment suspension was separated
from the grinding media. The pigment was isolated by filtration and
dried at 60C under reduced pressure.
The pigment so obtained which had a specific surface of about
70 m /g yielded upon dyeing enamels according to known methods
brilliant greenish blue shades of a high degree of purity and
tinctorial strength. The pigment was distinguished as compared
with known commercial brands by a good stability towards flocculation
and an excellent dispersibility in lacquering systems.
When used in book printing according to known methods, the
pigment so obtained yielded prints that were distinguished by a high
tinctorial strength and an especially high purity of shade.
When the grinding medium used in the fine distribution is 150
parts of methanol or 150 parts of glycolmonomethyl ether or 120 parts
of acetone, instead of the 150 parts of isopropanol, pigments of the
same quality were obtained.
When the additive used for the fine distribution is 1.5 parts
of 1.8 parts of CuPc-monosulfonic acid instead of the 1.2 parts of
CuPc-monosulfonic acid, pigments of the same quality were obtained.
However, when instead of 1.2 parts of ~uPc-monosulfonic acid 3 parts
of this compound were used, pigments were obtained which were dis-
tinguished in the dyeing of lacquers by a very high transparency and
an excellent tinctorial strength, but which had a minor dispers-
ibility.
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lC~73880
E X A M P L E 7:
30 Parts of the pure CuPc of the ~-modification obtained according
to Example 6 and 1.2 parts of CuPc-monosulfonic acid were ground together
with 1,200 parts of glass beads of 3 mm diameter and a mixture of 139 parts
of water and 11 parts of isobutanol in a porcelain mill during 24 hours on
a "Vibratom" vibration table. Then, thc pigment suspension was separated
from the grinding bodies. The pigment was isolated by filtration and dried ~-
at 60C under reduced pressure.
Upon dyeing enamels according to known methods, the pigment so
prepared yielded brilliant greenish blue shades of a high degree of purity
and tinctorial strength. The pigment was distinguished by an excellent
dispersibility in lacquers.
When instead of the mixture of 139 parts of water and 11 parts of
isobutanol a mixture of 75 parts of water and 75 parts of isopropanol or
a mixture of 112 parts of water and 38 parts of isopropanol was used,
pigments were obtained which had the same quality.
Pigments of the same quality were also obtained when the fine
distribution was not performed discontinuously on a "Vibratom" vibration
table, but continuously on a continuous vibration mill or a continuous
roller mill.
E X A M P L E 8:
30 Parts of the pure CuPc of the ~-modification obtained according
to Example 6 and 3 parts of the sodium salt of CuPc-monosulfonic acid
were ground together with 150 parts of isopropanol and 1,200 parts of
quartzite beads of 2 mm diameter in a porcelain mill during 24 hours on
a "Vibratom" vibration table. ThenJ the pigment suspension was separated
from the grinding bodies and the pigment was isolated by distilling off
the solvent.
- 16 -
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1~7388~)
When dyeing enamels accordin~ to known methods, the pigment so
obtained yielded brilliant greenish blue shades of high tinctorial
strength. The pigment was distinguished by a very good dispersibility in
lacquers.
Pigments of the same quality were obtained when instead of 3 parts
of the sodium salt 3 parts of the barium salt or 3 parts of the ammonium
salt of CuPc-monosulfonic acid were used as additive.
E X A M P L E 9:
32.6 Parts of unsubstituted crude CuPc ~in the form of a 93%
commercial product) were introduced into 300 parts of 86% sulfuric acid
and then stirred for 4 hours at 70 - 80C in a nitrogen atmosphere. The
coarse crystals of CuPc-sulfate so obtained were filtered off after cooling
to room temperature, washed with 80% sulfuric acid and then hydrolized by
introducing the filter cake into 300 parts of water. The CuPc was filtered
off, washed with water until neutral and dried at 100C. 30 Parts of
coarse crystals of pure CuPc of the ~-modification were obtained.
For the rearrangement of the phases and the fine distribution at the
same time the pure CuPc of the ~-modification was ground after the
addition of 1.5 parts of CuPc-monosulfonic acid together with 150 parts of
xylene and 1,200 parts of glass beads of 3 mm diameter in a porcelain mill
during 24 hours on a "Vibratom" vibration table. Then, the pigment
suspension was separated from the grinding bodies. The pigment was
- isolated by filtration and dried at 60C under reduced pressure.
The pigment so obtained, which is in the form of the ~-crystal
modification yielded upon dyeing enamels colorings of high tinctorial
strength. The pigment was distinguished by a very good dispersibility
in lacquers.
.` :
- 17 -
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1~7388~1
E X A M P L E 10:
95 Parts of unsubstituted crude CuPc ~in form of a 95% commercial
product) and 7.5 parts of CuPc-monosulfonic acid were dissolved together
in 1,000 parts of 96% sulfuric acid. At 70 to 80C, 116 parts of water were
added dropwise and the suspension was stir~ed at 70 - 80C for 4 hours
under a nitrogen atmosphere. After cooling to room temperature, the
CuPc-sulfate was filtered off, washed with 80% sulfuric acid and the
filter cake was hydrolized in 1,000 parts of water. To the suspension,
100 parts of chlorobenzene were added and the suspension was boiled under
reflux for 4 hours. The chlorobenzene was eliminated by steam distillation.
The pigment was isolated by filtration, washed with water until neutral and
dried at 100C.
30 Parts of the pure pigment so obtained which was in the form of the
~-modification and contained about 6% of CuPc-monosulfonic acid, were ground
with 150 parts of isopropanol and 1,200 parts of glass beads of 3 mm
diameter in a porcelain mill during 24 hours on a "Vibratom" vibration
table. Then, the pigment was isolated by filtration and dried at 60C
under reduced pressure.
When dyeing enamels, the pigment so obtained yielded brilliant
greenish blue shades of a high degree of purity and tinctorial strength.
The pigment was distinguished by a very good dispersibility in lacquers.
E X A M P L E 11:
30 Parts of the pure CuPc of the ~-modification obtained according
to Example 6 were subjected after the addition of a mixture of 0.9 part of
CuPc-monosulfonic acid and 0.3 part of CuPc-disulfonic acid to the process
of fine distribution as described in Example 6. The pigment obtained
corresponded to that obtained according to Example 6 with respect to its
quality.
- - 18 -
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16~7388~)
E X A M P L E 12:
30 Parts of t~e pure CuPc of the ~-modification according to
Example 6 and 1.5 parts of N,N'-bis~dodecyl)-CuPc-disulfonamide (prepared
by reacting dodecyl amine with the dichloride of CuPc-disulfonic acid)
were ground together with 1,200 parts of glass beads of 3 mm diameter and
150 parts of acetone in a porcelain mill during 20 hours on a "Vibratom"
vibration table. The pigment suspension was then separated from the grinding
bodies and the pigment was isolated by evaporation.
When dyeing enamels according to known methods the pigment so obtained
yielded brilliant greenish blue shades of a high degree of purity and
tinctorial strength. The pigment dyestuff was distinguished by an excellent
dispersibility.
When instead of 1.5 parts of the above sulfonamide - additive a
mixture of 1.2 parts of N,N'-bis-(isobutyl~-CuPc-disulfonamide and 0.3 part
of N,N',N"-tris-(isobutyl)-CuPc-trisulfonamide was used as additive, a
pigment was obtained which had the same quality.
E X A M P L E 13:
30 Parts of the pure CuPc of the ~-modification obtained according
to Example 6 and 1.5 parts of N,N'-bis-(phenyl)-CuPc-disulfonamide were
ground together with 1,200 parts of glass beads of 3 mm diameter and 150
parts of isopropanol in a porcelain mill during 24 hours on a "Vibratom"
vibration table. Then, the pigment suspension was separated from the
grinding bodies. The pigment was isolated by filtration and dried at 60C
under reduced pressure.
When dyeing enamels, the pigment so obtained yielded brilliant
greenish blue shades of a high degree of purity and tinctorial strength.
The pigment was distinguished by a very good dispersibility in lacquering
systems.
- 19 -
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1~73880
Pigments of the same quality were obtained, when instead of N,N'-
bis-(phenyl)-CuPc-disulfonamide one of the following compounds was used
as additive:
CuPc-disulfonamide
N,N'-bis-(di-n-butyl)-CuPc-disulfonamide
N,N'-bis-(a-ethylhexyl)-CuPc-disulfonamide
N,N'-bis-(octadecyl)-CuPc-disulfonamide
N,N'-bis-(~-aminoethyl)-CuPc-disulfonamide
CuPc-disulfonic acld diphenyl ester
E X A M P L E 14:
30 Parts of the pure CuPc of the ~-modification obtained according to
Example 6 and a mixture of 1.3 parts of N,N'-bis-(di-n-butyl)-CuPc-
; Disulfonamide and 0.3 part of N,N',N"-tris-(di-n-butyl)-CuPc-trisulfonamide
(prepared by reacting a corresponding mixture of CuPc-disulfochloride and
CuPc-trisulfochloride with di-n-butyl amine) were ground together with
1,200 parts of glass beads of 2 mm diameter, 139 parts of water and 11
parts of isobutanol in a porcelain mill during 24 hours on a "Vibratom"
vibration table. The pigment suspension was separated from the grinding
bodies and the pigment was isolated by filtration and dried at 60C under
reduced pressure.
When dyeing enamels, the pigment so obtained yielded brilliant
shades of a high degree of purity and tinctorial strength.
When dyeing polyvinyl chloride according to known methodsJ the pigment
was easily dispersible and yielded dyeings that were distinguished by a
high tinctorial strength and an extraordinary degree of purity of the shade.
When the fine distribution was performed not discontinuously on a
vibration table but continuously in a bead mill of the type "~olinex" of
Messrs. Netzsch with glass beads of 1 mm diameter, a pigment was obtained
- - 20 -
;
:
.
73880
which had the same quality.
E X A M P L E 15:
32.6 Parts of unsubstituted crude CuPc (in the form of a 93%
commercial product) were introduced into 300 parts of 86% sulfuric acid and
stirred during 4 hours at 70 - 80C in a nitrogen atmosphere. The coarse
crystals of the CuPc-sulfate so formed were filtered off after cooling to
room temperature, washed with 80% sulfuric acid and then hydrolized by
introducing the filter cake into 300 parts of water. The CuPc was filtered
off and washed with water until neutral.
To obtain the rearrangement of the phases from the~-modification into
the ~-modification, the moist filter cake was introduced into 300 parts of
water, 30 parts of chlorobenzene were added and the mixture was stirred under
reflux during 4 hours. The chlorobenzene was removed by steam distillation.
The pigment suspension was filtered and the filter cake was dried at 100C.
30 Parts of pure CuPc of the ~-modification were obtained.
For the fine filter distribution, the 30 parts of the pure CuPc so
obtained were ground after the addition of 3 parts of tris-(isobutylamino-
methyl)-CuPc ~prepared by reacting tris-(chloromethyl)-CuPc with isobutyl
amine) together with 150 parts of isopropanol and 1,200 parts of glass beads
of 3 mm diameter in a porcelain mill during 24 hours on a "Vibratom"
vibration table. Then, the pigment suspension was separated from the
grinding bodies. The pigment was isolated by filtration and dried a~
60C under reduced pressure.
When dyeing enamels according to known methods, the pigment so
obtained yielded brilliant greenish blue shades of a high degree of purity
and tinctorial strengthJ and an excellent fastness to light and to
~' atmospheric influences. The pigment was distinguished by a good stability
towards flocculation and excellent dispersibility in lacquering systems.
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~738~3~
When the grinding medium in the fine distribution was 150 parts of
methanol, 150 parts of glycolmonomethyl ether or 120 parts of acetone instead
of the 150 parts of isopropanol, the pigment obtained had the same quality.
The same result was obtained when the fine distribution was not
effected discontinuously on a "Vibratom" vibration table, but continuously
on a continuously operating vibration mill or roller mill
E X A M P L E 16:
30 Parts of the pure CuPc of the ~-modification prepared according to
Example 15 and a mixture of 0.5 part of bis-(isobutylaminomethyl)CuPc and
2 parts of tris-(isobutylaminomethyl)-CuPc and 0.5 part of tetrakis-~iso-
butylaminomethyl)-CuPc were introduced into 150 parts of isopropanol and
stirred until a homogeneous suspension had formed. The suspension was
ground continuously on a continuously operating bead mill of the type
"Molinex" with the use of glass beads of 1 mm diameter. The pigment was
isolated by distilling of the solvent. The pigment so obtained corresponded
to that obtained according to Example 15 with respect to its quality.
E X A M P L E 17:
~!
30 Parts of the pure CuPc of the ~-modification obtained according
to Example 15 and 3 parts of tris-(n-octylaminomethyl)-CuPc were ground
i 20 together with 150 parts of acetone and 1,200 parts of quartzite beads of
3 mm diameter in a porcelain mill during 24 hours on a "Vibratom" vibration
table. The pigment suspension was separated from the grinding bodies, the
pigment was isolated by filtration and dried at 60C under reduced pressure.
The pigment so prepared yielded according to known methods enamels of
brilliant greenish blue shades of a high degree of purity and tinctorial
strength. The pigment was distinguished by a very good dispersibility in
lacquers.
- 22 -
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73880
Pigments of the same quality were obtained, when instead of tris-
(n-octylaminomethyl)-CuPc one of the following compounds was used as
additive:
tris-(n-propylaminomethyl)-CuPc
tris-(n-butylaminomethyl)-CuPc
tris-(n-hexylaminomethyl)-CuPc
bis-(~-aminoethylaminomethyl)-CuPc
tris-(n-dodecylaminomethyl)-CuPc
tris-(N-phenylaminomethyl)-CuPc
tris-(N-methyl-N-phenyl-aminomethyl)-CuPc
When instead of 3 parts of tris-(n-octylaminomethyl)-CuPc only 1.5
parts of this compound were used as additive, a pigment was obtained which
also yielded brilliant greenish blue shades of a high degree of purity
and tinctorial strength.
E X A M P L E 18:
30 Parts of the pure CuPc of the ~-modification prepared according
to Example 15 and 2 parts of tris-(phthalimidomethyl)-CuPc (prepared by
reacting CuPc with N-methylolphthalimide in sulfuric acid) were ground
together with 1,200 parts of glass beads of 3 mm diameter and 150 parts of
isopropanol in a porcelain mill during 24 hours on a "Vibratom" vibration
~I table. The pigment suspension was separated from the grinding bodies, the
pigment was isolated by filtration and dried at 60C under reduced pressure.
The pigment so obtained dyed enamels brilliant greenish blue shades of
a high degree of purity and tinctorial strength. The pigment was distin-
guished by an excellent dispersibility in lacquers.
E X A M P L E 19:
30 Parts of the pure CuPc of the ~-modification prepared according
to Example 15 and 1.5 parts of tris-(n-octylaminomethyl)-CuPc were ground
- 23 -
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1~73880
together with 139 parts of water, 11 parts of isobutanol and 1,200 parts of
glass beads of 2 mm diameter in a porcelain mill during 24 hours on a "Vibra-
tom" vibration table. The pigment suspension was separated from the grinding
bodies, the pigment was isolated by filtration and dried at 60C under
reduced pressure.
; The pigment so obtained dyed enamels brilliant shades of a high
degree of purity and tinctorial strength. When dyeing polyvinyl chloride
according to known methods, the pigment was easily dispersible and yielded
dyeings of high tinctorial strength which were distinguished by a high
degree of purity.
When instead of the mixture of 139 parts of water and 11 parts of
isopropanol a mixture of 75 parts of water and 75 parts of isopropanol or
a mixture of 112 parts of water and 38 parts of isopropanol was used as
grinding medium, pigments were obtained that had the same qumllty.
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