U.S. patent application number 09/993840 was filed with the patent office on 2002-05-30 for use of improved cyan pigments in electrophotographic toners and developers, powder coatings and inkjet inks.
Invention is credited to Baur, Ruediger, Geisenberger, Josef, Harz, Andreas, Macholdt, Hans-Tobias, Menzel, Heidemarie, Michel, Eduard.
Application Number | 20020062763 09/993840 |
Document ID | / |
Family ID | 7911677 |
Filed Date | 2002-05-30 |
United States Patent
Application |
20020062763 |
Kind Code |
A1 |
Macholdt, Hans-Tobias ; et
al. |
May 30, 2002 |
Use of improved cyan pigments in electrophotographic toners and
developers, powder coatings and inkjet inks
Abstract
The present invention relates to the use of a CuPc composition
consisting essentially of CuPc, e.g., C.I. Pigment Blue 15:3, and a
hydroxymethylphthalimido CuPc, as a colorant in electrophotographic
toners and developers, powders and powder coating materials,
electret materials, inkjet inks, and color filters, wherein the
phthalocyanines have a particle morphology with an average
length-to-width ratio of more than 2.5:1.
Inventors: |
Macholdt, Hans-Tobias;
(Darmstadt-Eberstadt, DE) ; Baur, Ruediger;
(Eppstein, DE) ; Michel, Eduard; (Frankfurt,
DE) ; Geisenberger, Josef; (Sulzbach, DE) ;
Menzel, Heidemarie; (Bad Soden, DE) ; Harz,
Andreas; (Waghaeusel, DE) |
Correspondence
Address: |
CLARIANT CORPORATION
4331 CHESAPEAKE DR
ATTN: INDUSTRIAL PROPERTY DEPT
CHARLOTTE
NC
28216
US
|
Family ID: |
7911677 |
Appl. No.: |
09/993840 |
Filed: |
November 16, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09993840 |
Nov 16, 2001 |
|
|
|
09591747 |
Jun 12, 2000 |
|
|
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Current U.S.
Class: |
106/31.49 ;
540/123; 540/140 |
Current CPC
Class: |
G03G 9/0918 20130101;
G02B 5/22 20130101; C09D 5/035 20130101; C09D 11/32 20130101; C09B
67/0035 20130101 |
Class at
Publication: |
106/31.49 ;
540/123; 540/140 |
International
Class: |
C09D 011/02; C09B
047/04; C09B 062/00; C09B 067/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 18, 1999 |
DE |
199 27 835.0 |
Claims
1. The use of a copper phthalocyanine composition consisting
essentially of a compound of the formula (I) 12and of a compound of
the formula (II) 13as a colorant in electrophotographic toners and
developers, powders and powder coating materials, electret
materials, inkjet inks, and color filters, wherein the compounds of
the formulae (I) and (II) have a particle morphology with an
average length-to-width ratio of more than 2.5:1.
2. The use as claimed in claim 1, wherein the average
length-to-width ratio is from 3:1 to 6:1.
3. The use as claimed in claim 1, wherin the quantitative ratio of
the compound of the formula (I) to the compound of the formula (II)
is from 90:10 to 99:1% by weight.
4. The use as claimed in claim 1, wherein the compound of the
formula (I) is C.I. Pigment Blue 15:3.
5. The method as claimed in claim 1, wherein the phthalocyanine
composition is shaded with a further organic color pigment, an
inorganic pigment, or a dye.
6. The method as claimed in claim 1, wherein the phthalocyanine
composition is used in combination with a charge control agent from
the group of the triphenylmethanes; ammonium and immonium
compounds; iminium compounds; fluorinated ammonium and fluorinated
immonium compounds; biscationic acid amides; polymeric ammonium
compounds; diallylammonium compounds; aryl sulfide derivatives;
phenol derivatives; phosphonium compounds and fluorinated
phosphonium compounds; calix(n)arenes; cyclically linked
oligosaccharides and their derivatives, interpolyelectrolyte
complexes; polyester salts; metal complex compounds,
salicylate-nonmetal complexes, aluminum-azo complexes,
.alpha.-hydroxycarboxylic acid-metal and -nonmetal complexes; boron
complexes of 1,2-dihydroxyaromatics, 1,2-dihydroxyaliphatics or
2-hydroxy-1-carboxyaromatics; benzimidazolones; and azines,
thiazines or oxazines.
7. The use as claimed in claim 1 in liquid toners or powder
toners.
8. An electrophotographic toner or developer comprising a toner
binder, from 0.1 to 60% by weight of shaded or unshaded
phthalocyanine composition, and from 0 to 20% by weight based in
each case on the overall weight of the toner or developer, of a
charge control agent from the class of the triphenyimethanes,
ammonium and immonium compounds; fluorinated ammonium and immonium
compounds; biscationic acid amides; polymeric ammonium compounds;
diallylammonium compounds; aryl sulfide derivatives; phenol
derivatives; phosphonium compounds and fluorinated phosphonium
compounds; calix(n)arenes; cyclodextrins; polyester salts; metal
complex compounds; cyclooligosaccharide-boron complexes,
interpolyelectrolyte complexes; benzimidazolones; azines, thiazines
or oxazines.
9. An electrophotographic toner or developer comprising a toner
binder, from 0.5 to 20% by weight of shaded or unshaded
phthalocyanine composition, and from 0.1 to 5% by weight based in
each case on the overall weight of the toner or developer, of a
charge control agent from the class of the triphenylmethanes,
ammonium and immonium compounds; fluorinated ammonium and immonium
compounds; biscationic acid amides; polymeric ammonium compounds;
diallylammonium compounds; aryl sulfide derivatives; phenol
derivatives; phosphonium compounds and fluorinated phosphonium
compounds; calix(n)arenes; cyclodextrins; polyester salts; metal
complex compounds; cyclooligosaccharide-boron complexes,
interpolyelectrolyte complexes; benzimidazolones; azines, thiazines
or oxazines.
10. A powder or powder coating material comprising an acrylic resin
or polyester resin containing epoxy, carboxyl or hydroxyl groups,
or a combination of such resins, from 0.1 to 60% by weight of
shaded or unshaded phthalocyanine composition, and from 0 to 20% by
weight based in each case on the overall weight of the powder or
powder coating material, of a charge control agent from the class
of the triphenyi-methanes, ammonium and immonium compounds;
fluorinated ammonium and immonium compounds; biscationic acid
amides; polymeric ammonium compounds; diallylammonium compounds;
aryl sulfide derivatives; phenol derivatives phosphonium compounds
and fluorinated phosphonium compounds; calix(n)arenes;
cyclodextrins; polyester salts; metal complex compounds;
cyclooligosaccharide-boron complexes, interpolyelectrolyte
complexes; benzimidazolones; azines, thiazines or oxazines.
11. A powder or powder coating material comprising an acrylic resin
or polyester resin containing epoxy, carboxyl or hydroxyl groups,
or a combination of such resins, from 0.5 to 20% by weight of
shaded or unshaded phthalocyanine composition, and from 0.1 to 5%
by weight based in each case on the overall weight of the powder or
powder coating material, of a charge control agent from the class
of the triphenyl-methanes, ammonium and immonium compounds;
fluorinated ammonium and immonium compounds; biscationic acid
amides; polymeric ammonium compounds; diallylammonium compounds;
aryl sulfide derivatives; phenol derivatives; phosphonium compounds
and fluorinated phosphonium compounds; calix(n)arenes;
cyclodextrins; polyester salts; metal complex compounds;
cyclooligosaccharide-boron complexes, interpolyelectrolyte
complexes; benzimidazolones; azines, thiazines or oxazines.
12. An inkjet ink comprising from 0.5 to 15% by weight of a copper
phthalocyanine composition as set forth in claim 1.
13. An inkjet ink as claimed in claim 10, which is a microemulsion
ink, a solvent-based inkjet ink or a hot-melt inkjet ink.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to the use of a certain copper
phthalocyanine composition in electrophotographic toners and
developers, powder coating materials and inkjet inks.
[0002] In electrophotographic recording techniques a "latent charge
image" is produced on a photoconductor. This latent charge image is
developed by applying an electrostatically charged toner which is
then transferred, for example, to paper, textiles, foils or plastic
and is fixed by means, for example, of pressure, radiation, heat,
or the action of a solvent. Typical toners are one- or
two-component powder toners (also called one- or two-component
developers); furthermore special toners are employed, examples
being magnetic or liquid toners, latex toners, polymerization
toners and microencapsulated toners based on wax, for example.
[0003] One measure of the quality of a toner is its specific charge
q/m (charge per unit mass). In addition to the sign and level of
the electrostatic charge, the rapid attainment of the desired
charge level and the constancy of this charge over a prolonged
activation period, in particular, is a decisive quality criterion.
Moreover, the insensitivity of the toner to climatic effects such
as temperature and atmospheric humidity is another important
criterion for its suitability.
[0004] Both positively and negatively chargeable toners are used in
photocopiers, laser printers, LED (light emitting diode), LCS
(liquid crystal shutter) printers or other digital printers based
on electrophotography, depending on the type of process and type of
equipment.
[0005] In order to obtain electrophotographic toners or developers
with either a positive or a negative charge it is common to add
charge control agents. As the color-imparting component in color
toners, use is typically made of organic color pigments. As
compared with dyes, color pigments have considerable advantages on
account of their insolubility in the application medium, such as
improved thermal stability and lightfastness, for example.
[0006] On the basis of the principle of subtractive color mixing it
is possible, with the aid of the three primary colors yellow, cyan
and magenta, to reproduce the entire spectrum of colors visible to
the human eye. Exact color reproduction is only possible if the
particular primary color satisfies the precisely defined color
requirements. If this is not the case, some shades cannot be
reproduced and the color contrast is inadequate.
[0007] In the case of full color toners, the three toners yellow,
cyan and magenta must not only meet the precisely defined color
requirements but must also be matched exactly to one another in
their triboelectric properties, since they are transferred one
after another in the same device.
[0008] 6- and 7-color systems are likewise known. The base colors
are red, green, blue, cyan, magenta, yellow and black. it is also
possible to produce full color prints by the Pantone
Hexachrome.RTM. system with the colors cyan, magenta, yellow,
black, orange and green.
[0009] It is known that colorants may have a long-term effect on
the triboelectric charging of toners. As a result, it is normally
not possible simply to add the colorants to a toner base
formulation once prepared. It may instead be necessary to prepare a
specific formulation for each colorant, with the nature and amount
of the required charge control agent being tailored specifically.
This approach is, correspondingly, laborious and in the case of
color toners for process color is just another difficulty to add to
those already described above.
[0010] Furthermore, it is important for practical use that the
colorants possess high thermal stability and good dispersibility.
Typical temperatures for incorporation of colorants into the toner
resins are between 100.degree. C. and 200.degree. C. when using
compounders or extruders. Accordingly, a thermal stability of
200.degree. C., or even better 250.degree. C., is a great
advantage. It is also important that the thermal stability is
maintained over a prolonged period (about 30 minutes) and in
different binder systems. Typical toner binders are resins formed
by addition polymerization, polyaddition and polycondensation, such
as styrene, styrene-acrylate, styrene-butadiene, acrylate,
polyester and phenol-epoxy resins, polysulfones and polyurethanes,
individually or in combination.
[0011] Fundamentally there is a need for color pigments possessing
a very high degree of transparency, good dispersibility and a low
inherent electrostatic effect: as far as possible a neutral
inherent triboelectric effect. Neutral inherent triboelectric
effect means that the pigment has very little or no effect on the
inherent electrostatic charging of the resin and readily follows a
defined charge established by means, for example, of charge control
agents.
[0012] Transparency is of great importance since, in the case of
full color copies or in printing, the colors yellow, cyan and
magenta are copied or printed over one another, the sequence of
colors depending on the device. Consequently, if an overlying color
is not sufficiently transparent, then the underlying color is
unable to show through to a sufficient extent and the color
reproduction is distorted. In the case of copying or printing on
sheets for overhead projection use, transparency is even more
important, since in this case a lack of transparency even in just
one color makes the whole of the projected image gray.
[0013] The cyan shade, furthermore, is of great importance since it
is used both in four-color printing and in 6- or 7-color
printing.
SUMMARY OF THE INVENTION
[0014] The object of the present invention is to provide an
improved cyan pigment satisfying the above requirements for use in
electrophotographic toners and developers, powder coating
materials, inkjet inks, color filters, and electret fibers.
[0015] This object has surprisingly been achieved by the use of the
copper phthalocyanine composition defined hereinbelow.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0016] The present invention provides for the use of a copper
phthalocyanine composition consisting essentially of a compound of
the formula (I) 1
[0017] and of a compound of the formula (II) 2
[0018] as a colorant in electrophotographic toners and developers,
powders and powder coating materials, electret materials, inkjet
inks, and color filters, wherein the compounds of the formulae (I)
and (II) have a particle morphology with an average length-to-width
ratio of more than 2.5:1, preferably from 3:1 to 6:1.
[0019] The relative proportions of the compound of the formula (I)
to the compound of the formula (II) can fluctuate within wide
limits; for example, from 0.1:99.9% by weight to 99.9:0.1% by
weight. Preference is given to compositions of from 80 to 99.5% by
weight of the compound of the formula (I) and from 0.5 to 20% by
weight of the compound of the formula (II). Particular preference
is given to compositions of from 90 to 99% by weight of the
compound of the formula (I) and from 1 to 10% by weight of the
compound of the formula (II).
[0020] The compound of the formula (I) is known per se (DE-A-2 432
564) and is in commerce under the designation C.I. Pigment Blue 15.
The .beta.-modification is preferred, being known under the names
C.I. Pigment Blue 15:3 and 15:4. Also suitable in principle,
however, are the .alpha.-modification (C.I. Pigment Blue 15:1 and
15:2, from 0.5 to 1 Cl) and the ,-modification (C.I. Pigment Blue
15:6).
[0021] The compound of the formula (II) is known per se and can be
prepared in analogy to EP-A-0 508 704 by reacting the
N-methylol-phthalimide with a phthalocyanine.
[0022] Conventional C.I. Pigment Blue 15, especially 15:3,
possesses a very pronounced intrinsic triboelectric effect (e.g.,
U. Schlosser et al., Society of Imaging Science and Technology,
11th Congress on Advances in Non-impact Printing Technology, Hilton
Head, S.C., Oct. 29-Nov. 11, 1995, Proceedings pp 110-112) which
can be overcome only with great effort and in many cases only
partly by means, for example, of adding charge control agents,
which is very expensive.
[0023] It is novel and surprising that the phthalocyanine
composition used in accordance with the invention and having the
stated particle morphology possesses a very stable and neutral
intrinsic triboelectric effect and exhibits a significant
improvement in respect of transparency and dispersibility. The
intrinsic triboelectric effect is the influence of the colorant on
the electrostatic charging of the binder. The normal aim is that
the colorant should not alter the charging behavior of the binder.
Ideally, irrespective of the-addition of colorant, the binder has
the same charge per mass after the same activation time. The fact
that a needle-shaped (acicular) particle morphology in the copper
phthalocyanine composition of the invention leads to a stable and
neutral intrinsic triboelectric effect was very surprising, since
it is known from EP-A-0 813 117 that the colorant used therein has
an intrinsic triboelectric effect which is more stable and neutral
the less the extent to which the pigment particles are
needle-shaped, i.e., the greater the extent to which the pigment
particles are cube-shaped--in other words, precisely the opposite
of the present case. It was further surprising that the copper
phthalocyanine composition of the invention despite its
needle-shaped particle morphology has high flocculation stability,
ready dispersibility, in aqueous and nonaqueous media, and high
color strength and luster. Ease of dispersibility is of importance
not only for toners, powder coating materials and electret
materials but also, in particular, for inkjet inks, since in this
case the pigment dispersion must be extremely fine in order not to
block the very fine printer nozzles.
[0024] Furthermore, the copper phthalocyanine composition thus
prepared has a high negative particle surface charge: for example,
in the range from -60 to -300 mV/mg, in particular from -60 to -120
mV/mg.
[0025] The phthalocyanine composition of the invention can be
prepared by finely dividing crude copper phthalocyanine with a
suitable grinding apparatus--for example, on a ballmill or
beadmill--subjecting the finely divided copper phthalocyanine to a
solvent finish in aqueous-organic or organic medium at a
temperature of from 20 to 200.degree. C. for a period of time
permitting crystal growth, e.g., at least 1/2 hour, preferably from
2 to 10 hours, and then adding the phthalimidomethylene CuPc.
Examples of suitable organic media are alcohols, such as n- or
i-butanol, ketones, such as methyl ethyl ketone, methyl isobutyl
ketone or diethyl ketone and carboxamides, such as DMF or
dimethylacetamide.
[0026] As well as in electrophotographic toners and developers, the
copper phthalocyanine composition can also be used as colorant in
powders and coating materials, especially in triboelectrically or
electrokinetically sprayed powder coating materials as used to coat
the surfaces of articles made, for example, from metal, wood,
textile material, paper or rubber. The powder coating or powder
obtains its electrostatic charge in general by one of the two
following methods:
[0027] a) in the case of the corona method, the powder coating
material or powder is guided past a charged corona and is charged
in the process;
[0028] b) in the case of the triboelectric or electrokinetic
method, the principle of frictional electricity is utilized.
[0029] Typical powder coating resins employed are epoxy resins,
carboxyl- and hydroxyl-containing polyester resins, polyurethane
resins and acrylic resins together with the customary hardeners.
Resin combinations are also used. For example, epoxy resins are
frequently employed in combination with carboxyl- and
hydroxyl-containing polyester resins.
[0030] Furthermore, the improved triboelectric behavior of the
colorant may result in an improvement in the electret properties in
the case of colored (pigmented) electret materials, typical
electret materials being based on polyolefins, halogenated
polyolefins, polyacrylates, polyacrylonitriles, polystyrenes or
fluoropolymers, examples being polyethylene, polypropylene,
polytetrafluoroethylene and perfluorinated ethylene and propylene,
or on polyesters, polycarbonates, polyamides, polyimides, polyether
ketones, on polyarylene sulfides, especially polyphenylene
sulfides, on polyacetals, cellulose esters, polyalkylene
terephthalates, and mixtures thereof. Electret materials have
numerous fields of use and may acquire their charge through corona
charging or triboelectric charging (ref.: G. M. Sessler,
"Electrets", Topics in Applied Physics, Vol. 33, Springer Verlag,
New York, Heidelberg, 2nd Ed., 1987).
[0031] Furthermore, the improved triboelectric influence of the
colorant may result in improved separation characteristics of
colored (pigmented) polymers which are separated by electrostatic
methods (Y. Higashiyau, J. of Electrostatics, 30, pages 203-212,
1993). Accordingly, the inherent triboelectric effect of pigments
is important for the mass coloring of plastics as well. The
inherent triboelectric effect is also significant in process or
processing steps which involve intense frictional contact, examples
being spinning processes, film-drawing processes or other shaping
processes.
[0032] Furthermore, the phthalocyanine composition is also suitable
as a colorant for color filters, both for subtractive and for
additive color generation (P. Gregory "Topics in Applied Chemistry:
High Technology Application of Organic Colorants" Plenum Press, New
York 1991, pp. 15-25).
[0033] A task frequently encountered in connection with
electrophotographic color toners, powder coating materials or
inkjet inks is to shade the hue and adapt it to the requirements of
the specific application. Particularly appropriate for this purpose
are further organic color pigments, inorganic pigments, and dyes.
Further organic color pigments can be used in mixtures with the
copper phthalocyanine composition in concentrations between 0.01
and 50% by weight, preferably between 0.1 and 25% by weight and,
with particular preference, between 0.1% and 15% by weight, based
on the copper phthalocyanine composition. The further organic color
pigments can be from the group of the azo pigments or polycyclic
pigments.
[0034] Preferred blue and/or green pigments for shading are the
respective other copper phthalocyanines, such as C.I. Pigment Blue
15, 15:1, 15:2, 15:3, 15:4, 15:6, P. Blue 16 (metal-free
phthalocyanine), or phthalocyanines with aluminum, nickel, iron or
vanadium as the central atom, and also triarylcarbonium pigments,
such as Pigment Blue 1, 2, 9, 10,14, 62 and Pigment Green 1, 4 and
45. Mixtures of one or more components are likewise suitable.
Relatively large steps in hue are possible, for example, using
orange pigments such as P.O. 5, 62, 36, 34, 13, 43 and 71; yellow
pigments such as P.Y. 12, 13, 17, 83, 93, 122, 155, 180, 174, 185
and 97; red pigments such as P.R. 48, 57, 122, 146, 184, 186, 202,
207, 209, 254, 255, 270 and 272; or violet pigments such as P.V. 1
and 19. The mixtures can be prepared in the form of powders, by
mixing presscakes, spray-dried presscakes or masterbatches and by
dispersion (extrusion, kneading, roll-mill processes, bead mills,
Ultra-Turrax) in the presence of a carrier material in solid or
liquid form (aqueous and nonaqueous inks) and by flushing in the
presence of a carrier material. If the colorant is used with high
proportions of water or solvent
[0035] (>5%), then mixing can also take place at elevated
temperatures with vacuum assistance.
[0036] Particularly appropriate for increasing the brightness but
also for shading the hue are mixtures with organic dyes. Preferred
such dyes are water-soluble dyes, such as direct, reactive and acid
dyes, and also solvent-soluble dyes, such as solvent dyes, disperse
dyes and vat dyes. Specific examples that may be mentioned are C.I.
Reactive Yellow 37, Acid Yellow 23, Reactive Red 23, 180, Acid Red
52, Reactive Blue 19, 21, Acid Blue 9, Direct Blue 199, Solvent
Yellow 14, 16, 25, 56, 62, 64, 79, 81, 82, 83, 83:1, 93, 98, 133,
162, 174, Solvent Red 8,19, 24, 49, 89, 90, 91, 92, 109, 118, 119,
122, 124, 127, 135, 160, 195, 212, 215, Solvent Blue 44, 45,
Solvent Orange 41,60, 63, Disperse Yellow 64, Vat Red 41, and
Solvent Black 45, 27.
[0037] It is also possible to use dyes and pigments having
fluorescent properties, such as .RTM.Luminols (Riedel-de Haen), in
concentrations of from 0.0001 to 10% by weight, preferably from
0.001 to 5% by weight and, with very particular preference, between
0.01 and 1%, based on the phthalocyanine composition, in order, for
example, to produce anticounterfeit toners.
[0038] Inorganic pigments, such as TiO.sub.2 or BaSO.sub.4, are
used in mixtures for lightening. Also suitable are mixtures with
effect pigments, such as pearl luster pigments, Fe.sub.2O.sub.3
pigments (.RTM.Paliochromes) and pigments based on cholesteric
polymers, for example, which give different perceived colors
depending on the viewing angle.
[0039] The copper phthalocyanine composition employed in accordance
with the invention can also be combined with charge control agents,
providing either positive or negative control, in order to achieve
defined charging performance. The simultaneous use of positive and
negative charge control agents is a further option.
[0040] Examples of suitable charge control agents are:
triphenylmethanes; ammonium and immonium compounds; iminium
compounds; fluorinated ammonium and fluorinated immonium compounds;
biscationic acid amides; polymeric ammonium compounds;
diallylammonium compounds; aryl sulfide derivatives; phenol
derivatives; phosphonium compounds and fluorinated phosphonium
compounds; calix(n)arenes; cyclically linked oligosaccharides
(cyclodextrins) and their derivatives, especially boron ester
derivatives, interpolyelectrolyte complexes (IPECs); polyester
salts; metal complex compounds, especially carboxylate-metal,
salicylate-metal and salicylate-nonmetal complexes, aluminum-azo
complexes, .alpha.-hydroxycarboxylic acid-metal and -nonmetal
complexes; boron complexes of 1,2-dihyd roxyaromatics, 1,2-d
ihydroxyaliphatics or 2-hydroxy-1-carboxyaromatics;
benzimidazolones; and azines, thiazines or oxazines which are
listed in the Colour Index as Pigments, Solvent Dyes, Basic Dyes or
Acid Dyes.
[0041] Examples of charge control agents which can be combined
individually or in combination with one another with the
phthalocyanine composition of the invention are:
[0042] triarylmethane derivatives such as, for example:
[0043] Colour Index Pigment Blue 1, 1:2, 2, 3, 8, 9, 9:1, 10, 10:1,
11, 12, 14, 18, 19, 24, 53, 56, 57, 58, 59, 61, 62, 67 or, for
example, Colour Index Solvent Blue 2, 3, 4, 5, 6, 23, 43, 54, 66,
71, 72, 81, 124, 125, and also the triarylmethane compounds listed
in the Colour Index under Acid Blue and Basic Dye, provided they
are suitable in terms of their thermal stability and processing
properties, such as, for example, Colour Index Basic Blue 1, 2, 5,
7, 8, 11, 15, 18, 20, 23, 26, 36, 55, 56, 77, 81, 83, 88, 89,
Colour Index Basic Green 1, 3, 4, 9, 10, with Colour Index Solvent
Blue 125, 66 and 124 in turn possessing special suitability. Colour
Index Solvent Blue 124, in the form of its highly crystalline
sulfate or of the trichlorotriphenylmethyltetrachloroaluminat- e,
is particularly suitable. Metal complexes bearing the CAS Numbers
84179-66-8 (chromium azo complex), 115706-73-5 (iron azo complex),
31714-55-3 (chromium azo complex), 84030-55-7 (chromium salicylate
complex), 42405-40-3 (chromium salicylate complex) and also the
quaternary ammonium compound CAS No. 116810-46-9 and also aluminum
azo complex dyes, metal carboxylates and sulfonates.
[0044] Examples of charge control agents of the triphenylmethane
series that are highly suitable for the production of electret
fibers are the compounds described in DE-A-1 919 724 and DE-A-1 644
619.
[0045] Of particular interest are triphenylmethanes as described in
U.S. Pat. No. 5,051,585, especially those of the formula (2) 3
[0046] in which R.sup.1 and R.sup.3 are phenylamino groups, R.sup.2
is an m-methylphenylamino group, and the radicals R.sup.4 to
R.sup.10 are all hydrogen.
[0047] Also suitable are ammonium and immonium compounds as
described in U.S. Pat. No. 5,015,676, and fluorinated ammonium and
immonium compounds as described in U.S. Pat. No. 5,069,994,
especially those of the formula (3) 4
[0048] in which
[0049] R.sup.13 is perfluorinated alkyl of 5 to 11 carbon
atoms,
[0050] R.sup.23, R.sup.33 and R.sup.43 are identical or different
and are alkyl of 1 to 5, preferably 1 to 2, carbon atoms, and
[0051] Y.sup.- is a stoichiometric equivalent of an anion,
preferably of a tetrafluoroborate or tetraphenylborate anion.
[0052] Also suitable are biscationic acid amides, as described in
WO 91/10172.
[0053] Further suitable compounds are diallylammonium compounds as
described in DE-A-4,142,541 and also the polymeric ammonium
compounds obtainable therefrom of the formula (6), as described in
DE-A-4 029 652 or DE-A-4 103 610 5
[0054] in which n has a value corresponding to molecular weights of
from 5000 to 500,000 g/mol, preferably molecular weights of from
40,000 to 400,000 g/mol.
[0055] Also suitable are aryl sulfide derivatives as described in
DE-A-4 031 705, especially those of the formula (7) 6
[0056] in which
[0057] R.sup.17, R.sup.27, R.sup.37 and R.sup.47 are identical or
different alkyl groups of 1 to 5, preferably 2 or 3, carbon atoms,
and
[0058] R.sup.57 is one of the divalent radicals --S--, --S--S--,
--SO--and --SO.sub.2.
[0059] For example, R.sup.17 to R.sup.47 are propyl groups and
R.sup.57 is the group --S--S--.
[0060] Also suitable are phenol derivatives as described in EP-A-0
258 651, especially those of the formula (8) 7
[0061] in which
[0062] R.sup.18 and R.sup.38 are alkyl or alkenyl groups of 1 to 5,
preferably 1 to 3, carbon atoms and R.sup.28 and R.sup.48 are
hydrogen or alkyl of 1 to 3 carbon atoms, preferably methyl.
[0063] Also suitable are phosphonium compounds and fluorinated
phosphonium compounds, as described in U.S. Pat. No. 5,021,473 and
in U.S. Pat. No. 5,147,748.
[0064] Other suitable compounds include calix(n)arenes, as
described in EP-A-0 385 580, EP-A-0 516 434 and in Angew. Chemie
(1993), 195, 1258.
[0065] Further suitable compounds are metal complex compounds, such
as chromium-, cobalt-, iron-, zinc- or aluminum-azo complexes or
chromium-, cobalt-, iron-, zinc- or aluminum-salicylic or boric
acid complexes of the formula (14) 8
[0066] in which
[0067] M* is a divalent central metal atom, preferably a chromium,
aluminum, iron, boron or zinc atom,
[0068] R.sup.114 and R.sup.214 are identical or different
straight-chain or branched alkyl groups of 1 to 8, preferably 3 to
6, carbon atoms, an example being tert-butyl.
[0069] Also suitable are benzimidazolones as described in EP-A-0
347 695.
[0070] Further suitable compounds are cyclically linked
oligosaccharides as described in DE-A4 418 842.
[0071] Further suitable compounds are polymer salts, as described
in DE-A-4 332 170, especially the product described in Example 1
thereof.
[0072] Also suitable are cyclooligosaccharide compounds, as are
described, for example, in DE-A-1 971 1260, which are obtainable by
reacting a cyclodextrin or cyclodextrin derivative with a compound
of the formula 9
[0073] in which R.sup.1 and R.sup.2 are alkyl, preferably
C.sub.1-C.sub.4-alkyl.
[0074] Also suitable are interpolyelectrolyte complexes as are
described, for example, in DE-A-197 32 995. Particularly suitable
such compounds are those featuring a molar ratio of polymeric
cationic to polymeric anionic groups of from 0.9:1.1 to
1.1:0.9.
[0075] Further suitable compounds, especially for use in liquid
toners (Handbook of Imaging Materials, 1991, Marcel Dekker, Inc.,
Chapter 6, Liquid Toner Technology), are surface-active ionic
compounds and what are known as metal soaps.
[0076] Particularly suitable are alkylated arylsulfonates, such as
barium petronates, calcium petronates, barium
dinonylnaphthalenesulfonates (basic and neutral), calcium
dinonylsulfonate or sodium dodecylbenzenesulfonate, and
polyisobutylenesuccinimides (Chevron's .RTM.Oloa 1200). Soya
lecithin and N-vinylpyrrolidone polymers are also suitable. Also
suitable are sodium salts of phosphated mono- and diglycerides of
saturated and unsaturated substituents, AB diblock copolymers of A:
polymers of 2-(N,N)-dimethylaminoethyl methacrylate quaternized
with methyl p-toluenesulfonate, and B: poly-2-ethylhexyl
methacrylate.
[0077] Also suitable, especially in liquid toners, are divalent and
trivalent carboxylates, especially aluminum tristearate, barium
stearate, chromium stearate, magnesium octoate, calcium stearate,
iron naphthalite and zinc naphthalite.
[0078] Suitability extends to chelating charge control agents, as
described in EP 0 636 945 A1, metallic (ionic) compounds, as
described in EP 0 778 501 A1, phosphate metal salts, as described
in JA 9 (1997)-106107, azines of the following Colour Index
Numbers: C.I. Solvent Black 5, 5:1, 5:2, 7, 31 and 50; C.I. Pigment
Black 1, C.i. Basic Red 2 and C.I. Basic Black 1 and 2.
[0079] The combination of phthalocyanine composition of the
invention and charge control agents can be effected by means of
physical mixing of the respective powders, presscakes or
masterbatches, or by appropriate application to the surface of the
pigment (pigment coating). Both components can also advantageously
be added in the case of polymerization toners, for which the binder
is polymerized in the presence of the copper phthalocyanine
composition of the invention and, if appropriate, of the charge
control agent, or can be used in the preparation of liquid toners
in high-boiling inert solvents, such as hydrocarbons.
[0080] The copper phthalocyanine composition of the invention is
also suitable for aqueous-based electrocoagulation toners.
[0081] The invention therefore also provides an electrophotographic
toner or developer comprising a toner binder, from 0.1 to 60% by
weight, preferably from 0.5 to 20% by weight, of shaded or unshaded
phthalocyanine composition, and from 0 to 20% by weight, preferably
from 0.1 to 5% by weight, based in each case on the overall weight
of the toner or developer, of a charge control agent from the class
of the triphenylmethanes, ammonium and immonium compounds;
fluorinated ammonium and immonium compounds; biscationic acid
amides; polymeric ammonium compounds; diallylammonium compounds;
aryl sulfide derivatives; phenol derivatives; phosphonium compounds
and fluorinated phosphonium compounds; calix(n)arenes;
cyclodextrins; polyester salts; metal complex compounds;
cyclooligosaccharide-boron complexes, interpolyelectrolyte
complexes; benzimidazolones; azines, thiazines or oxazines.
[0082] It is also possible to add further components to the toner,
such as waxes, which may be of animal, vegetable or mineral origin,
synthetic waxes, or mixtures thereof. Waxes are understood to be
substances which are kneadable at 20.degree. C., ranging from firm
to hard and fragile, from coarse to finely crystalline, and from
translucent to opaque, but not grasslike. In addition, a light
stabilizer can be added to the toner. Subsequently, free flow
agents, such as TiO.sub.2 or highly disperse silica, can also be
added to the toner.
[0083] The invention additionally provides a powder or powder
coating material comprising an acrylic resin or polyester resin
containing epoxy, carboxyl or hydroxyl groups, or a combination of
such resins, from 0.1 to 60% by weight, preferably from 0.5 to 20%
by weight, of shaded or unshaded phthalocyanine composition, and
from 0 to 20% by weight, preferably from 0.1 to 5% by weight, based
in each case on the overall weight of the powder or powder coating
material, of a charge control agent selected from the preferred
compounds and classes mentioned above for electrophotographic
toners.
[0084] The phthalocyanine composition used in accordance with the
invention is judiciously incorporated homogeneously, for example by
extrusion or kneading, or added during the polymerization of the
binder, in a concentration of from 0.1 to 60% by weight, preferably
from 0.5 to 20% by weight and, with particular preference, from 0.1
to 5.0% by weight, based on the overall mixture, into the binder of
the respective toner (liquid or dry), developer, powder coating
material, electret material or polymer for electrostatic
separation. In this context, the copper phthalocyanine composition
and, if appropriate, the abovementioned charge control agent can
also be added in the form of dried and ground powders, dispersions
or suspensions in, for example, organic and/or inorganic solvents,
presscakes (which can be used, for example, for the flush process),
spray-dried presscakes, masterbatches, preparations, made-up
pastes, and as compounds applied to suitable carriers, examples
being kieselguhr, TiO.sub.2, Al.sub.2O.sub.3, from aqueous or
nonaqueous solution, or in some other form. The phthalocyanine
content in the presscake and masterbatch is usually between 5 and
70% by weight, preferably between 20 and 50% by weight.
Furthermore, the phthalocyanine composition can also be used as a
highly concentrated presscake, especially as a spray-dried
presscake, in which case the phthalocyanine content is between 25
and 95% by weight, preferably between 50 and 90% by weight.
[0085] The level of the electrostatic charge of the
electrophotographic toners or of the powder coatings into which the
pigment of the invention is homogeneously incorporated cannot be
predicted and is measured on standard test systems under identical
conditions (identical dispersion times, identical particle size
distribution, identical particle morphology) at approximately
20.degree. C. and 50% relative atmospheric humidity. The
electrostatic charging of the toner is carried out by fluidization
with a carrier, i.e. a standardized friction partner (3 parts by
weight of toner per 97 parts by weight of carrier) on a bed of
rolls (150 revolutions per minute). Subsequently, the electrostatic
charging is measured on a customary qlm measurement setup.
[0086] The triboelectric spraying of the powders or powder coating
materials is carried out using a spraying apparatus with a standard
spray pipe and a star-shaped inner rod at maximum powder throughput
with a spray pressure of 3 bar. For this purpose, the article to be
sprayed is suspended in a spray booth and is sprayed from a
distance of about 20 cm directly from the front, without any
further movement of the spraying apparatus. The charge of each
sprayed powder is then measured using a "Device for measuring the
triboelectric charge of powders" from Intec (Dortmund). To carry
out the measurement, the antenna of the measuring device is held
directly in the cloud of powder emerging from the spraying
apparatus. The current strength resulting from the electrostatic
charge of powder coating material or powder is displayed in .mu.A.
The deposition rate is determined subsequently in % by differential
weighing of the sprayed and of the deposited powder coating
material.
[0087] The transparency and color strength in toner binder systems
is investigated as follows: 30 parts by weight of the pigmented
test toner are stirred with a dissolver (5 minutes at 5000 rpm)
into 70 parts by weight of a base varnish (consisting of 15 parts
by weight of the respective toner resin and 85 parts by weight of
ethyl acetate).
[0088] The test toner varnish produced in this way is knife-coated
onto suitable paper (e.g., letterpress paper), using a manual
coater, against a standard pigmented varnish produced in the same
way. A suitable size for the coater bar is, for example, K bar N 3
(=24 .mu.m coat thickness). To allow better determination of
transparency, the paper has printed on it a black bar, and the
transparency and color strength differences in terms of dL values
are determined in accordance with DIN 55 988 or evaluated in
accordance with the test procedure from Pigments Marketing,
Clariant GmbH "Visuelle und Farbmetrische Bewertung von Pigmenten"
[Visual and calorimetric evaluation of pigments] version 3, 1996
(No. 1/1).
[0089] It has also been found that the copper phthalocyanine
composition is suitable as a colorant in aqueous (including
microemulsion inks) and nonaqueous ("solvent-based") inkjet inks,
and in those inks which operate in accordance with the hot-melt
technique.
[0090] Microemulsion inks are based on organic solvents, water and,
if desired, an additional hydrotropic substance (interface
mediator). Nonaqueous inks contain essentially organic solvents
and, if desired, a hydrotropic substance.
[0091] The present invention additionally provides inkjet recording
liquids which comprise the phthalocyanine composition.
[0092] The finished recording liquids generally include from 0.5 to
15% by weight, preferably from 1.5 to 8% by weight, of the copper
phthalocyanine composition, based on the overall weight of the
recording liquid.
[0093] Microemulsion inks consist essentially of from 0.5 to 15% by
weight, preferably from 1.5 to 8% by weight of the phthalocyanine
composition, from 5 to 99% by weight of water and from 0.5 to 94.5%
by weight of organic solvent and/or hydrotropic compound.
[0094] "Solvent based" inkjet inks consist essentially of from 0.5
to 15% by weight of the phthalocyanine composition and from 85 to
94.5% by weight of an organic solvent and/or hydrotropic compound.
Carrier materials for "solvent based" inkjet inks can be
polyolefins, natural rubber and synthetic rubber, polyvinyl
chloride, vinyl chloride/vinyl acetate copolymers, polyvinyl
butyrates, wax/latex systems or combinations thereof which are
soluble in the "solvent".
[0095] Hot-melt inks are based predominantly on organic compounds,
such as waxes, fatty acids, fatty alcohols or sulfonamides, which
are solid at room temperature and liquefy when heated, the
preferred melting range lying between about 60.degree. C. and about
140.degree. C.
[0096] The invention also provides a hot-melt inkjet ink consisting
essentially of from 20 to 90% by weight of wax and from 1 to 10% by
weight of the phthalocyanine composition, unshaded or shaded by
further colorants, from 0 to 20% by weight of an additional polymer
(as "colorant dissolver"), from 0 to 5% by weight of dispersing
auxiliaries, from 0 to 20% by weight of viscosity modifiers, from 0
to 20% by weight of plasticizers, from 0 to 10% by weight of tack
additive, from 0 to 10% by weight of transparency stabilizer
(prevents, e.g., crystallization of waxes), and from 0 to 2% by
weight of antioxidant.
[0097] The solvents present in the recording liquids described
above can comprise an organic solvent or a mixture of such
solvents. Examples of suitable solvents are mono- or polyhydric
alcohols, their ethers and esters, e.g., alkanols, especially those
of 1 to 4 carbon atoms, such as methanol, ethanol, propanol,
isopropanol, butanol and isobutanol; dihydric or trihydric
alcohols, especially those of 2 to 5 carbon atoms, examples being
ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, glycerol,
diethylene glycol, dipropylene glycol, triethylene glycol,
polyethylene glycol, tripropylene glycol, polypropylene glycol;
lower alkyl ethers of polyhydric alcohols, such as, for example,
ethylene glycol monomethyl, monoethyl or monobutyl ether,
triethylene glycol monomethyl or monoethyl ether; ketones and
ketone alcohols such as, for example, acetone, methyl ethyl ketone,
diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone,
cyclopentanone, cyclohexanone and diacetone alcohol; amides, such
as dimethylformamide, dimethylacetamide, N-methylpyrrolidone,
toluene and n-hexane, for example.
[0098] Water used to prepare the recording liquids is used
preferably in the form of distilled or deionized water.
[0099] Hydrotropic compounds, which may also act as solvents,
include for example formamide, urea, tetramethylurea,
.epsilon.-caprolactam, ethylene glycol, diethylene glycol,
triethylene glycol, polyethylene glycol, butyl glycol,
methyl-Cellosolve, glycerol,
[0100] N-methylpyrrolidone, 1,3-diethyl-2-imidazolidinone,
thiodiglycol, sodium benzenesulfonate, Na xylenesulfonate, Na
toluenesulfonate, sodium cumenesulfonate, Na dodecylsulfonate, Na
benzoate, Na salicylate or sodium butyl monoglycol sulfate.
[0101] The recording liquids of the invention may also include
other customary additives, examples being preservatives, cationic,
anionic or nonionic surface-active substances (surfactants and
wetting agents), and also viscosity regulators, e.g., polyvinyl
alcohol, cellulose derivatives, or water-soluble natural or
synthetic resins as film formers and/or binders for increasing the
adhesive strength and abrasion resistance.
[0102] Amines, such as ethanolamine, diethanolamine,
triethanolamine, N,N-dimethylethanolamine or diisopropylamine, for
example, serve primarily to increase the pH of the recording
liquid. They are normally present in the recording liquid in a
proportion of from 0 to 10%, preferably from 0.5 to 5%, by
weight.
[0103] The inkjet inks of the invention can be prepared by
dispersing the copper phthalocyanine composition--in the form of a
powder, an aqueous or nonaqueous preparation, a suspension or a
presscake--into the microemulsion medium or into the aqueous or
nonaqueous medium or into the wax for preparing a hot-melt inkjet
ink. The presscake can also be a highly concentrated presscake,
especially a spray-dried presscake.
[0104] In addition to printing on paper, natural and synthetic
fiber materials, films or plastics, inkjet inks can also be used on
glass, ceramic, concrete and the like.
EXAMPLES
[0105] In the examples below, parts and percentages are by weight.
CuPc denotes copper phthalocyanine.
Synthesis Example 1
[0106] 1.1 Preparation of Crude Copper Phthalocyanine
[0107] The synthesis of C.I. Pigment Blue 15:3 (copper
phthalocyanine, .beta. modification) takes place, for example, as
decribed in DE-A-24 32 564, Example 1. The crude copper
phthalocyanine produced in this way is subsequently suspended in
water and ground in a laboratory ball mill for 24 hours.
[0108] 1.2 Preparation of the Phthalimidomethyl-CuPc Additive
[0109] In a 1 liter reaction vessel, 216 ml of water, 90 g of
formalin (35% strength) and 120 g of phthalimide are combined with
stirring at room temperature and subsequently heated to 100.degree.
C. A clear solution is formed, which is cooled. The reaction
product which precipitates is filtered off, washed and dried.
[0110] Yield (dry): 136 g of hydroxymethylphthalimide.
[0111] In a 1 liter reaction vessel, 32 g of crude copper
phthalocyanine from Synthesis Example 1.1 are added slowly with
stirring to 240 ml of 98% strength sulfuric acid at 35.degree.
C.
[0112] Subsequently, 40 g of the hydroxymethylphthalimide are added
slowly. The reaction mixture is heated to about 80.degree. C., then
cooled to room temperature and poured into an ice-water mixture.
The precipitate is filtered and washed.
[0113] Yield: 260 g of presscake (20% solids content) of
phthalimidomethyl-CuPc.
[0114] 1.3 Solvent Finish
[0115] In a 500 ml reaction vessel, 50 g of the crude CuPc
described under 1.1 are stirred at room temperature into 100 ml of
water. Then 100 ml of methyl ethyl ketone are added and the mixture
is boiled at reflux (74.degree. C.) for 2 hours with stirring. The
solvent is distilled off under atmospheric pressure (about
80.degree. C.) with the simultaneous slow addition of 100 ml of
H.sub.2O. Subsequently, at about 80.degree. C., 6.25 g of the
phthalimidomethyl-CuPc presscake described under 1.2 are added. The
reaction mixture thus obtained is stirred for several hours at
60-80.degree. C. The end product is filtered off, washed, filtered
off with suction and subsequently dried and ground.
[0116] Yield: 50 g of blue pulverulent copper phthalocyanine
composition.
[0117] Product characterization:
1 pH 6.5 Residual moisture content (baking flask) 0.3% Residual
salt content: 70 .mu.S/cm BET surface area: 61.3 m.sup.2/g Particle
size: d.sub.25: 0.08 .mu.m d.sub.50: 0.1 .mu.m d.sub.75: 0.13 .mu.m
Particle morphology (length-to-width ratio) Total sample: 3.06:1
Fine fraction 2.87:1 Middle fraction 3.19:1 Coarse fraction
3.13:1
[0118] Particle size and particle morphology are determined by
means of an electron micrograph of the pigment powder. For this
purpose the pigment is dispersed for 15 minutes in water and
subsequently applied by spraying. The micrographs are taken at
13,000 and 29,000 times magnification.
[0119] Thermalstability: A DTA (differential thermoanalysis,
3.degree. C./min heating rate, closed glass ampule) shows a
thermalstability of distinctly more than 200.degree. C.
[0120] X-ray diffraction diagram (CuK.sub..A-inverted.
radiation):
[0121] 2 theta (s=strong, m=moderate, w=weak):
2 Width at half peak height 2 Theta Intensity (relative intensity)
(2 theta) 7.0 100% 0.28 9.2 76% 0.28 10.5 14% 0.28 12.5 13% 0.26
18.2 17% 0.2 18.5 17% 0.2 21.4 12% 0.2 23.0 11% 0.22 23.8 40% 0.24
26.2 28% 0.26 28.0 15% 0.24 30.4 16% 0.25
[0122] Transparency
[0123] In a toner resin (bisphenol A based polyester) an improved
transparency is measured (24 .mu.m layer thickness), the pigmented
test toner being prepared as in Application Example 2.
[0124] Relative to the standard indicated in Synthesis Example 2
(comparative), a transparency higher by 4-5 points is found after
adjusting for equal color strength.
[0125] Evaluation of the transparency differences in accordance
with test specification 1/1:1trace, 2somewhat; 3markedly;
4distinctly; 5substantially; 6significantly more transparent.
[0126] Color strength: Relative to the standard indicated in
Synthesis Example 2, the pigment from Synthesis Example 1 is 10%
stronger in color.
[0127] Particle Surface Charge
[0128] The electrokinetic particle surface charge is determined as
described in Chimia 48 (1994) 516-517 and the literature cited
therein. For a measured sample volume of 2 ml and a pigment
concentration of 5 g/l, the corresponding pigment particle surface
charge is obtained in mV/mg, the measurements being taken in each
case in the acid range, in the alkaline range and at the intrinsic
pH of the substance sample:
3 pH mV/mg acidic (4.1) -60 intrinsic pH (6.5) -71 alkaline (10.0)
-93
Synthesis Example 2 (Comparative Example)
[0129] The pigment used is .RTM.Hostaperm Blue B2G (C.I. Pigment
Blue 15:3, unsubstituted copper phthalocyanine) which is commonly
used in numerous toners and is prepared, for example, in accordance
with DE-A-3 023 722. The CuPc additive was not added.
4 Pigment characterization pH 6.4 Residual moisture content (baking
flask) 0.2% Residual salt content: 50 .mu.S/cm BET surface area:
50.2 m.sup.2/g Particle size: d.sub.25: 0.07 .mu.m d.sub.50: 0.09
.mu.m d.sub.75: 0.11 .mu.m Particle morphology (length-to-width
ratio) Total sample: 2.67:1 Fine fraction 2.33:1 Middle fraction
2.62:1 Coarse fraction 2.96:1
Synthesis Example 3 (Comparative Example)
[0130] 20 g of the crude CuPc described under Synthesis Example 1.1
are introduced into 300 ml of 66.5% strength sulfuric acid at 350C.
The suspension is stirred at 350C for 2.5 hours and then poured
into 320 ml of water. The mixture is heated to 80.degree. C. and
stirred at 80.degree. C. for 1 hour. It is then filtered and washed
with water in order to extract the sulfuric acid.
[0131] The presscake is stirred together with water to form a
readily stirrable suspension, and 10.7 g of 20% strength
phthalimidomethyl-CuPc presscake are added at room temperature. The
mixture is then heated to 135.degree. C. under superatmospheric
pressure and stirred at 135.degree. C. for 7 hours. The product is
filtered at 60.degree. C., washed, dried at 80.degree. C. and
pulverized:
5 pH 6.5 Residual moisture content (baking flask) 0.3% Residual
salt content: 70 .mu.S/cm BET surface area: 49 m.sup.2/g Particle
size: d.sub.25: 0.08 .mu.m d.sub.50: 0.1 .mu.m d.sub.75: 0.17 .mu.m
Particle morphology (length-to-width ratio) Total sample: 1.62:1
Fine fraction 2.07:1 Middle fraction 1.92:1 Coarse fraction
1.38:1
[0132] Application Examples for Toners
[0133] 5 parts of the respective colorant are incorporated
homogeneously using a kneading apparatus into 95 parts of a toner
binder (polyester resin based on bisphenol A, .RTM.Almacryl T500)
over the course of 30 minutes. The product is then ground on a
universal laboratory mill and classified on a centrifugal
classifier. The desired particle fraction (from 4 to 25 .mu.m) is
activated with a carrier consisting of silicone-coated ferrite
particles of size 50 to 200 .mu.m (bulk density 2.75 g/cm.sup.3)
(FBM 96-100; from Powder Tech.).
[0134] Measurement is carried out on a conventional q/m measurement
setup. A sieve having a mesh size of 25 .mu.m is used to ensure
that no carrier is entrained when the toner is blown out. The
measurements are made at a relative atmospheric humidity of
approximately 50%. As a function of the activation period, the
following q/m values [.mu.C/g] are measured:
6 Appli- cation Ex- Activation period / q/m in [.mu.C/g] ample
Toner system 5 min 10 min 30 min 2 h 24 h 1 (resin Polyester resin
only, -20 -20 -17 -13 -8 line) no colorant 2 Polyester resin +5%
-19 -12 -8 -6 -4 colorant from Synthesis Ex. 1 3 Polyester resin
+5% -12 -9 -3 +2 +3 (com- colorant from para- Synthesis Ex. 2 tive)
4 Polyester resin +5% -18 -6 -3 -2 0 (com- colorant from para-
Synthesis Ex. 3 tive
[0135] It is found that the toner containing the colorant of the
invention (Application Example 2) best follows the charging
behavior of the resin line (Application Example 1).
Application Example 5
[0136] 5 parts of the colorant from Synthesis Example 1 and 1 part
of the charge control agent of the formula 10
[0137] are incorporated into a polyester toner binder and subjected
to measurement. As a function of the activation period, the
following q/m values are measured:
7 Activation period q/m [.mu.C/g] 5 min -13 10 min -11 30 min -10 2
h -9 23 h -9
[0138] Very good charging constancy over the entire activation
period is found.
Application Example 5
[0139] 5 parts of the colorant from Synthesis Example 1 and 1 part
of the charge control agent of the formula 11
[0140] are incorporated into a styrene-acrylate toner binder and
subjected to measurement.
[0141] As a function of the activation period, the following q/m
values are measured:
8 Activation period q/m [.mu.C/g] 5 min +2 10 min +3 30 min +4 2 h
+3 23 h +2
[0142] Very good charging constancy over the entire activation
period is found. Application Examples for inkjet inks
Application Example 7
[0143] 10 parts of a finely ground 50% pigment preparation with the
colorant from Synthesis Example 1 (5 parts) in polyvinyl
chloride/polyvinyl acetate copolymer (5 parts), the homogeneous
colorant dispersion being obtained by intensive kneading into the
copolymer, are introduced with stirring into a mixture of 80 parts
of methyl isobutyl ketone and 10 parts of 1,2-propylene glycol,
using a dissolver. An inkjet ink having high transparency,
lightfastness and good passage through the nozzles is obtained.
Application Example 8
[0144] 5 parts of colorant from Synthesis Example 1, in the form of
a 40% ultrafine aqueous pigment preparation, are admixed with
stirring (paddle stirrer or dissolver) first with 75 parts of
deionized water and then with 6 parts of .RTM.Mowilith DM 760
(acrylate dispersion), 2 parts of ethanol, 5 parts of 1,2-propylene
glycol and 0.2 part of .RTM.Mergal K7. This gives an inkjet ink
having high transparency, high lightfastness and good passage
through the nozzles.
Application Example 9
[0145] 5 parts of colorant from Synthesis Example 1, in the form of
a 40% ultrafine aqueous pigment preparation, are admixed with
stirring first with 80 parts of deionized water and then with 4
parts of .RTM.Luviskol K 30 (polyvinylpyrrolidone, BASF), 5 parts
of 1,2-propylene glycol and 0.2 parts of .RTM.Mergal K7. This gives
an inkjet ink having high transparency, hight lightfastness and
good passage through the nozzles.
[0146] Application Example of Powder Coating Materials
Application Example 10
[0147] 5 parts of the colorant from Synthesis Example 1 are
incorporated homogeneously into 95 parts of a powder coating binder
based on a TGIC polyester, e.g., .RTM.Uralac P 5010 (DSM,
Netherlands). In order to determine the deposition rate, 30 g of
the test powder coating material are sprayed through a
triboelectric gun at a defined pressure.
9 Pressure [bar] Current [.mu.A] Deposition rate [%] 3 1.8 78
* * * * *