[0001] The present invention relates to a toner particles composition and to a developer
composition comprising these toner particles for developing electrostatic charge patterns
or images as claimed in claims 1 and 9, respectively.
[0002] In electrostatography a latent electrostatic charge image is made visible, i.e. developed,
by charged toner particles.
[0003] In electrophotography an electrostatic latent charge image is obtained with an electrophotographic
material typically comprising a coating of a photoconductive insulating material on
a conductive support. Said coating is given a uniform surface charge in the dark and
is then exposed to an image pattern of activating electromagnetic radiation such as
light or X-rays. The charge on the photoconductive element is dissipated in the irradiated
area to form an electrostatic charge pattern which is then developed with an electroscopic
marking material. The marking material or toner, as it is also called, whether carried
in an insulating liquid or in the form of a dry powder deposits on the exposed surface
in accordance with either the charge pattern or the discharge pattern as desired.
If the photoconductive element is of the reusable type, e.g. a selenium coated drum,
the toner image is transferred to another surface such as paper and then fixed to
provide a copy of the original.
[0004] A variety of electrostatic developers are available for use in developing electrostatic
charge patterns. A distinction is made between dry and liquid developers. According
to a known embodiment in dry developers carrier particles are mixed with toner particles
electrostatically adhering thereto. The carrier may comprise various materials and
as the name implies, serves as a medium for carrying the electrostatically responsive
marking particles to the charge pattern to be developed. Among the more common types
of carrier-toner developers are dry developers known for use in cascade development
as described e.g. in U.S.Patent Specification No. 2,618,552 and for use in magnetic
brush development as described e.g. in U.S.Patent Specification No. 3,003,462.
[0005] The cascade development technique is carried out by rolling or cascading across the
electrostatic latent image bearing surface, a developing mixture composed of relatively
large carrier particles, each having a number of electrostatically adhering toner
particles on its surface. As this mixture rolls across the image-bearing surface,
the toner particles are electrostatically deposited on the charged portions of the
image.
[0006] The magnetic brush development technique involves the use of magnetic means associated
with a developing mixture composed of magnetic carrier particles carrying a number
of smaller electrostatically adhering toner particles. In this technique the developer
composition is maintained during the development cycle in a loose, brushlike orientation
by a magnetic field surrounding, for example, a rotatable non-magnetic cylinder having
a means with magnetic poles mounted inside. The magnetic carrier particles are attracted
to the cylinder by the described magnetic field, and the toner particles are held
to the carrier particles by virtue of their opposite electrostatic polarity. Before
and during development, the toner acquires an electrostatic charge of a sign opposite
to that of the carrier material due to triboelectric charging derived from their mutual
frictional interaction. When this brushlike mass of magnetic carrier with adhering
toner particles is drawn across the surface bearing the electrostatic image, the toner
particles are electrostatically attracted to an oppositely charged latent image and
form a visible toner image corresponding to the electrostatic image. Since electrostatic
charge remains in the non-exposed areas of a photoconductive surface electrophotography
is inherently a direct positive process. In some instances, however, photocopying
requires the production of positive prints from photographic negatives.
[0007] Such is possible with line negatives as original due to the fringe effect. By the
fringe effect negative charges will be induced in the exposed areas which carried
originally positive charges but leaked off by the photoexposure. So, if a photoconductor
coating being originally overall charged positively has lost its positive charge in
correspondence with the line pattern of the original negative, charges of negative
sign will be induced in the exposed line pattern by the fringe effect of the still
surrounding positive charge pattern. Such makes that positively charged toner will
become attracted by said negative charges and a positive image will be developed with
respect to the original negative.
[0008] Reversal development of large image area will likewise be possible by applying a
bias voltage to a magnetic brush applicator which acting as a development electrode
induces when positively charged, through the conductive carrier particles a negative
charge in the discharged area of the previously positively charged photoconductor
coating (ref. R.M.Schaffert "Electrophotography" The Focal Press - London, New York
enlarged and revised edition 1975 p. 50-51 and T.P.Maclean "Electronic Imaging" Academic
Press - London, 1979 p.231).
[0009] In dry toner development systems the toner is normally a fine powder of natural or
synthetic resins having a colorant and a charge controlling agent dissolved or dispersed
therein.
[0010] Known positive charge controlling compounds for use in dry toners are dye bases and
salts thereof such as nigrosine dye base and salts described in GB-P 1,253,573. Such
charge controlling agents are usually added to the thermoplastic resin to be dispersed
in the resin in molten state. Upon cooling the mixture is micropulverized and the
particles with desired particle size separated e.g. by wind sifter.
[0011] Coloured charge controlling substances have the disadvantage that their colour interferes
with the colour intensionally given to the toner mass. For the obtaining of neutral
black or spectrally pure colours required in multicolour reproduction the inherent
colour of the charge controlling substance may form a serious obstacle. Therefore
preference is given to the use of colourless charge controlling substances.
[0012] According to the published unexamined Japanese patent application (Kokai) 6 0188-959
an electrostatic image developing toner contains as charge controlling agent a piperidine
compound corresponding to the following general formula (I) :
wherein : R₁, R₂, R₃ and R₄ are each 1-6C alkyl, R₅ is hydrogen or 1-5C alkyl, R₆
is hydrogen or 1-12C alkyl or 3-12C alkenyl, or 7-12C aralkyl; n is an integer of
1-4 and R₇ is acyl or N-substituted carbamoyl where n is 1, diacyl, dicarbamoyl or
carbonyl where n is 2, triacyl where n is 3 and tetraacyl where n is 4.
[0013] It is an object of the present invention to provide a particulate toner material
for developing electrostatic charge images which toner particles composition contains
a colourless transparent charge controlling agent that does not interfere with the
colouring agent of the toner material and also acts as stabilizing agent protecting
organic dyes against discolouration by the action of light, ultraviolet radiation
and the heat applied in thermal fixing of the toner image.
[0014] It is a further object of the present invention to provide such toner material wherein
the charge controlling agent yields a particularly high positive charge to the toner
particles and has a good miscibility or compatibility with the polymeric binder material
present in the toner material.
[0015] Other objects and advantages of the present invention will become clear from the
further description.
[0016] In accordance with the present invention an electrostatically attractable toner particles
composition for use in the development of latent electrostatic images is provided,
said toner particles acquiring in the presence of carrier particles a positive charge
by triboelectric contact electrification, said composition containing (a) thermoplastic
resin(s) as binder in combination with a colorant and a colourless charge controlling
agent, characterized in that said colourless charge controlling agent contains in
its molecular structure at least one polyalkyl substituted piperidine group and a
sterically hindered phenol group, and has the following general formula (A) :
wherein :
R¹ is hydrogen or alkyl having 1 to 4 carbon atoms,
R² is alkyl or hydroxyalkyl, each having 1 to 12 carbon atoms, alkenyl or alkynyl
each having 3 or 4 carbon atoms or aralkyl such as benzyl,
R³ is hydrogen or methyl,
R⁴ and R⁵ are each alkyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 8 carbon
atoms,
X is oxygen or NH,
Y is hydrogen, alkyl having 1 to 12 carbon atoms or -C
nH
nCOOR⁷, in which n is 0 or an integer from 1 to 10 and R⁷ is hydrogen, alkyl having
1 to 18 carbon atoms, especially methyl or ethyl, or Y is a substituent of the formula
:
wherein :
R¹ and R² are as defined above, or
Y is a substituent of the formula :
wherein :
R¹ and R² are as defined above, and R⁹ is hydrogen or alkyl having 1 to 4 carbon atoms,
especially methyl or ethyl,
m is 1 or 2, and
p is 0 or 1.
[0017] In the toner particles according to the present invention said colourless compound
is used preferably in an amount in the range of 0.5 to 5 % by weight with respect
to the total toner composition.
[0018] Typical representatives of compounds according to said general formula (A) wherein
X is oxygen are described in US-P 4,268,593 relating to recording material for colour
photography wherein said compounds are used as light stabilizers.
[0019] The synthesis methods for preparing said compounds can be found in US-P 4,198,334
and 4,268,593 and in German Offenlegungsschriften (DE-OS) Nos. 2,456,364, 2,647,452,
2,654,058 and 2,656,769.
[0020] For illustrative purposes the preparation of an ester compound according to the above
general formula (A) having the following structural formula (Z) is given hereinafter.
[0021] 23.3 g of butylmalonic acid bis(1,2,2,2,6,6-pentamethyl-4-piperidinyl) ester and
13.2 g of N-(3,5-di-tert-butyl-4-hydroxybenzyl)dimethylamine were dissolved in 200
ml toluene. After addition of 0.25 g of LiNH ₂, the mixture was refluxed for 15 minutes
to give butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl)
ester. Melting point : 147 °C.
[0022] Particularly high triboelectric positive charging of toner particles according to
the present invention is obtained with the compound according to the above structural
formula (Z).
[0023] The toner particle according to the present invention may be used as so-called mono-component
toner particles or in admixture with carrier particles.
[0024] The toner particles composition can be prepared by any conventional technique such
as spray drying a solution in a suitable volatile solvent or grinding a solidified
composition of homogeneously mixed ingredients including a thermoplastic binder, colorant
and a colourless positive charge-imparting polymeric amino compound(s) according to
said general formula (A).
[0025] The toner particles have preferably a particle size in the range of 3 to 30 µm, and
more preferably in the range of 5 to 20 µm.
[0026] It has been established experimentally that when the basic ring nitrogen atom of
the piperidine nucleus or nuclei according to the above general formula (A) is transformed
into a salt form by reaction with an acid or by quaternization the positive charge
controlling properties are maintained.
[0027] Although the colourless charge controlling substances are preferably present in dissolved
state in the thermoplastic resin binder of the toner, such is not strictly necessary.
When said substances are present in dispersed state the colour of the colorant is
not that vivid by the opalescent character of the dispersion. A "colloidal" dispersion
is mostly obtained when amino-salts and quaternary derivatives of the compounds according
general formula (A) are used.
[0028] When amino-salts or quaternary ammonium salts derived from the amines according to
the above general formula (A) are used the anion(s) of these salts may be of any type
known in the art. Suitable anions are e.g. hydroxyl (OH⁻), chloride, iodide, sulfate,
ZnCl⁻⁴, and tolusulfonate. The affinity of the anion with respect to the carrier particle
surface may play a role in the triboelectric charging [ref. the book "Electrophotography"
by R.M. Schaffert, The Focal Press - London and New York (1975), p. 559-560].
[0029] For lowering the Coulomb attraction of the anions and cations, which may be in favour
of the transfer of the anions of the toner particles to the carrier particles whereby
triboelectric charging is improved, preferably anions of relatively large size are
used, e.g. PF
and other large size anions such as the tetraphenylboride anion described for use
in liquid electrophoretic developers in US-P 4,525,446.
[0030] For obtaining a hard toner which is in favour of a longer developer lifetime because
"smearing" of the toner particles on the carrier particles becomes less, preference
is given to thermoplastic resins having a melting point in the range of 100 to 120°C,
glass transition temperature (Tg) larger than 60 °C, with in their structure a major
part by weight of aromatic groups, e.g. phenyl groups. Said polymers may contain a
minor part by weight of electron donating groups, e.g. alkylamino or arylamino groups
to further improve the positive chargeability of the toner.
[0031] The charge imparting compounds applied according to the present invention yield particularly
high positive charging when dissolved or dispersed in a thermoplastic binder being
a resin selected from the group consisting of a homopolymer and copolymer of styrene
wherein the styrene content is preferably at least 50 mole %. Preferred copolymers
of styrene for use in toner material according to the present invention are copolymers
of styrene-(meth)acrylic acid esters such as styrene-methyl acrylate copolymer, styrene-ethyl
acrylate copolymer, styrene-n-butyl acrylate copolymer, styrene-n-octyl acrylate copolymer,
styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-n-butyl
methacrylate copolymer, styrene-isobutyl methacrylate copolymer, styrene-n-octyl methacrylate
copolymer, styrene-heptadecyl methacrylate copolymer, copoly(styrene-butadiene), and
a copolymer of styrene including up to 25 % by weight of monomer units comprising
a dialkylamino group.
[0032] Preferred copolymers containing said group have the following structural formula
(B) :
wherein :
x is 83-87 % by weight
y is 0-4 % by weight
z is 13-17 % by weight,
and have a melting point (ring and ball method) in the range of 106 to 115°C.
[0033] Said copolymers which may be used separately or in combination can be prepared by
common addition polymerisation starting with the monomers involved.
[0034] In the particulate toner material according to the present invention the colorant
being a dye or pigment may be soluble or dispersable in the polymeric resin binder.
[0035] In order to obtain toner particles with sufficient optical density in the spectral
absorption region of the colorant, the colorant is used preferably in an amount of
at least 2 % by weight with respect to the total toner composition, more preferably
in an amount in the range of 5 to 15 % by weight.
[0036] For black toners preference is given to carbon black as a colorant.
[0037] Examples of carbon black and analogous forms therefor are lamp black, channel black,
and furnace black e.g. SPEZIALSCHWARZ IV (trade-name of Degussa Frankfurt/M, W.Germany)
and VULCAN XC 72 and CABOT REGAL 400 (trade-names of Cabot Corp. High Street 125,
Boston, U.S.A.).
[0038] The characteristics of preferred carbon blacks are listed in the following table
1.
[0039] Toners for the production of colour images may contain organic dyes or pigments of
the group of phthalocyanine dyes, quinacridone dyes, triaryl methane dyes, sulphur
dyes, acridine dyes, azo dyes and fluoresceine dyes. A review of these dyes can be
found in "Organic Chemistry" by Paul Karrer, Elsevier Publishing Company, Inc. New
York (1950).
[0040] Typical inorganic pigments include black iron(III) oxide, copper(II) oxide and chromium(III)
oxide powder, milori blue, ultramarine cobalt blue and barium permanganate.
[0041] In order to obtain toner particles having magnetic properties a magnetic or magnetizable
material may be added during the toner production.
[0042] Magnetic materials suitable for said use are magnetic or magnetizable metals including
iron, cobalt, nickel and various magnetizable oxides including (hematite) Fe₂O₃, (magnetite)
Fe₃O₄, CrO₂ and magnetic ferrites, e.g. these derived from zinc, cadmium, barium and
manganese. Likewise may be used various magnetic alloys, e.g. permalloys and alloys
of cobalt-phosphors, cobalt-nickel and the like or mixtures of any of these. Good
results can be obtained with about 30 % to about 80 % by weight of magnetic material
with respect to the resin binder of the toner.
[0043] In the preparation of the toner the colorant and optionally magnetic material may
be added in finely divided state to the mixture of molten resin binder while stirring
until a mixture of homogeneously dispersed or dissolved material in the resin melt
is obtained. The mixing temperature is e.g. in the range of 100 to 150°C.
[0044] After cooling, the solid mass obtained is crushed and ground e.g. in a hammer mill
followed by a jet-mill to an average particle size of 1 to 50 µm. The fraction having
a particle size between 3-30 µm separated e.g. by air sifter is used. The resulting
powder may not be tacky below 50°C.
[0045] For a given charge density of the charge-carrying surface the maximum development
density attainable with toner particles of a given size is determined by the charge/toner
particle mass ratio, which is determined substantially by the triboelectric charge
obtained by friction-contact with the carrier particles.
[0046] In a particular embodiment the toner according to the present invention is applied
in a carrier-toner mixture wherein the toner acquires a positive charge by frictional
contact with the carrier. The carrier-toner mixture is preferably applied to the surface
carrying a latent electrostatic image by cascade-, or magnetic brush development which
techniques are described in detail by Thomas L. Thourson in his article "Xerographic
Development Processes : A Review", IEEE Transactions on Electron Devices, Vol. ED-19,
No. 4, April 1972 p. 497-504.
[0047] Suitable carrier particles for use in cascade and for magnetic brush development
are described in GB-P 1,438,110.
[0048] The carrier particles are preferably at least 3 times larger in size than the toner
particles. For use in cascade development their particle size is preferably in the
range of 50 to 1000 µm.
[0049] The carrier particles may be made of iron or steel optionally provided with an oxide
skin. Other types of carriers are on the basis of magnetic material such as ferrites
or magnetite finely dispersed in a resin binder material, so-called composite type
carriers, examples of which are given in US-P 4,600,675 and published European patent
application 0 289 663. Iron or steel carrier beads may be subjected to special pretreatments
to enhance the triboelectric charging of the toner. Suitable coating-treatments of
carrier beads are described e.g. in said last mentioned GB-P 1,438,110.
[0050] In magnetic brush development the carrier particles are magnetically attractable.
Particularly suited are the iron bead carrier particles according to United States
Patent Specification 2,786,440, which particles have been washed free from grease
and other impurities and have a diameter of 1.52x10⁻¹ to 2.03x10⁻¹ mm.
[0051] In a preferred embodiment of the present invention the toner particles are mixed
with iron carrier beads of a diameter in the range of 50 to 200 µm having a thin iron
oxide skin. These carrier beads have almost a spherical shape and are prepared e.g.
by a process as described in GB-P 1,174,571.
[0052] The developer composition may for example contain 1 to 5 parts by weight of toner
particles per 100 parts by weight of carrier particles.
[0053] According to a particular embodiment the flowing properties of the developer are
improved by mixing the toner particles with a flow improving substance such as colloidal
silica particles and/or microbeads of a fluorinated polymer. The flow improving substance
is used e.g. in an amount of 0.05 to 1 % by weight with respect to the toner.
[0054] Colloidal silica has been described for that purpose in the GB-P 1,438,110. Particularly
useful is AEROSIL 300 [trade mark of Degussa, Frankfurt (M) W.Germany] for colloidal
silica having a specific surface area of 300 sq.m/g. The specific surface area can
be measured by a method described by Nelsen and Eggertsen in "Determination of Surface
Area Adsorption Measurements by Continuous Flow Method", Analytical Chemistry, Vol.
30, No. 8 (1958) 1387-1390.
[0055] Suitable fluorinated polymer beads for improving the flowing properties of the toner
as well as of the carrier particles are described in the United States Patent Specification
4,187,329. A preferred fluorinated polymer for said use is poly(tetrafluoroethylene)
having a particle size of 3 to 4 µm and melting point of 325-329°C. Such poly(tetrafluoroethylene)
is sold under the trade name HOSTAFLON TF-VP-9202 by Farbwerke Hoechst A.G. W.Germany.
[0056] An other fluorinated polymer useful for that purpose is polyvinylidene fluoride having
an average particle size of 5 µm sold under the trade name KYNAR RESIN 301 by Pennwalt
Corp. - Plastic div. England.
[0057] The colloidal silica and/or said fluorinated polymer particles are mixed preferably
with the toner in a proportion of 0.15 % to 0.075 % by weight. The toner becomes thereby
non-tacky and obtains a reduced tendency to form a film on the xerographic plates
or drums e.g. having a vapour-deposited coating of a photoconductive Se-As alloy on
a conductive substrate e.g. aluminium.
[0058] The following comparative example illustrates the present invention without, however,
limiting it thereto. All parts, ratios and percentages are by weight unless otherwise
stated.
Comparative Example
Toner preparation without colouring agent
[0059] A pseudo toner was prepared without colouring agent to check whether or not the incorporated
charge controlling agent yielded a clear mixture on melting with the elected resin
binder.
[0060] Two comparable colourless pseudo toners were prepared by mixing in the melt 5 parts
of a furtheron identified charge controlling substance with 95 parts of copolymer
of (styrene-n-butylmethacrylate)(65/35) having a ring and ball softening point : 123
°C which copolymer serves as thermoplastic binder. The mixture was melt-kneaded at
130°C for 30 minutes. Thereupon the mixture was cooled down to room temperature, crushed
and then pulverised by milling in a jet mill.
[0061] By wind sifter a toner particle fraction having an average particle size of 13 µm
was separated.
Developer preparation
[0062] An electroscopic developer was prepared by mixing 3% of the separated toner particles
with iron bead carrier particles having an iron oxide skin and average grain size
of 80 µm. The triboelectric charging of the resulting powder mixture was realized
by a 30 minutes agitation in a metal cylinder having a diameter of 6 cm, being filled
for approximately 30% by volume with said mixture and revolving at a speed of 60 rpm.
Measurement.
[0063] Different triboelectric charge measurement techniques are available all being based
on the separation of the toner particles from the admixed carrier particles and the
determination of the charge of the separated toner particles directly or indirectly.
Depending on the applied technique somewhat differing charge to mass ratio (Q/M) values
are obtained expressed in coulomb/gram (C/g). For obtaining comparable results the
same separation and measuring technique should be used with toner of the same average
particle size since the triboelectric charging is a surface phenomenon.
[0064] In the present example the separation of the toner from the carrier particles was
realized in a commercially available blow-off type powder charge measuring device.
By calculating the surface area of the pseudo toner for a given mass and using the
Q/M data from the resulting blow-off separation the charge density was calculated,
and expressed in C/cm ².
[0065] The results obtained with a charge controlling substance according to the structural
formula (Z) applied in the present invention and charge controlling compound No. 14
of the already mentioned published unexamined Japanese patent application (Kokai)
6 0188-959 having the following structure are mentioned in Table 2.
[0066] The pseudo toners obtained with said both charge controlling agents were perfectly
optically clear which proves their good compatibility with the applied resin binder.
1. Electrostatically attractable toner particles composition for use in the development
of latent electrostatic images, said toner particles acquiring in the presence of
carrier particles a positive charge by triboelectric contact electrification, said
composition containing (a) thermoplastic resin(s) as binder in combination with a
colorant and a colourless positive charge controlling agent, characterized in that
said colourless charge controlling agent contains in its molecular structure at least
one polyalkyl substituted piperidine group and a sterically hindered phenol group
and has the following general formula (A) :
wherein :
R¹ is hydrogen or alkyl having 1 to 4 carbon atoms,
R² is alkyl or hydroxyalkyl, each having 1 to 12 carbon atoms, alkenyl or alkynyl
each having 3 or 4 carbon atoms or aralkyl,
R³ is hydrogen or methyl,
R⁴ and R⁵ are each alkyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 8 carbon
atoms,
X is oxygen or NH,
Y is hydrogen, alkyl having 1 to 12 carbon atoms or -C
nH
nCOOR⁷, in which n is 0 or an integer from 1 to 10 and R⁷ is hydrogen, alkyl having
1 to 18 carbon atoms or Y is a substituent of the formula :
wherein :
R¹ and R² are as defined above, or
Y is a substituent of the formula :
wherein :
R¹ and R² are as defined above, and R⁹ is hydrogen or alkyl having 1 to 4 carbon atoms,
m is 1 or 2, and
p is 0 or 1.
2. Electrostatically attractable toner particles composition according to claim 1 or
2, wherein said colourless charge controlling agent is used in amount in the range
of 0.5 to 5 % by weight with respect to the total toner composition.
3. Electrostatically attractable toner particles composition according to any of the
preceding claims, wherein said colourless charge controlling agent is dissolved or
dispersed in a thermoplastic binder being a resin selected from the group consisting
of a homo- and copolymer of styrene wherein the styrene content is at least 50 mole
%.
4. Electrostatically attractable toner particles composition according to claim 3, wherein
said copolymer is selected from the group consisting of styrene-methyl acrylate copolymer,
styrene-ethyl acrylate copolymer, styrene-n-butyl acrylate copolymer, styrene-n-octyl
acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate
copolymer, styrene-n-butyl methacrylate copolymer, styrene-isobutyl methacrylate copolymer,
styrene-n-octyl methacrylate copolymer, styrene-heptadecyl methacrylate copolymer,
copoly(styrene-butadiene), and a copolymer of styrene including up to 25 % by weight
of monomer units comprising a dialkylamino group.
5. Electrostatically attractable toner particles composition according to any of claims
1 to 4, wherein the colorant is carbon black.
6. Electrostatically attractable toner particles composition according to any of claims
1 to 4, wherein the colorant is an organic dye or pigment selected from the group
consisting of phthalocyanine dyes, quinacridone dyes, triaryl methane dyes, sulphur
dyes, acridine dyes, azo dyes and fluoresceine dyes.
7. Electrostatically attractable toner particles composition according to any of the
preceding claims, wherein the composition further comprises a magnetic or magnetizable
material.
8. Electrostatically attractable toner particles composition according to any of the
claims 1 to 7, wherein the basic ring nitrogen atom of the piperidine group in the
compounds according to said general formula (A) has been transformed into salt form.
9. Developer composition comprising toner particles having the composition according
to any of the preceding claims in admixture with carrier particles suited for use
in cascade-, or magnetic brush development of latent electrostatic charge images.
10. Developer composition according to claim 9, wherein said carrier particles are at
least 3 times larger in size than the toner particles and have an average grain size
in the range of 50 to 1000 µm.
11. Developer composition according to claim 9 or 10, wherein the carrier particles are
made of iron or steel provided with an oxide layer.
1. Eine Zusammensetzung elektrostatisch anziehbarer Tonerteilchen für den Gebrauch in
der Entwicklung latenter, elektrostatischer Bilder, wobei diese Tonerteilchen in Anwesenheit
von Trägerteilchen durch triboelektrische Kontaktelektrisierung eine positive Ladung
erwerben, wobei diese Zusammensetzung ein oder mehrere thermoplastische Harze als
Bindemittel zusammen mit einem Farbstoff und einem farblosen Positivladungsregler
enthält, dadurch gekennzeichnet, daß der farblose Ladungsregler in seiner Molekularstruktur
zumindest eine polyalkylsubstituierte Piperidingruppe und eine sterisch behinderte
Phenolgruppe enthält und die folgende, allgemeine Formel (A) hat:
in der bedeuten:
R¹ ein Wasserstofatom oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen,
R² eine Alkylgruppe oder eine Hydroxyalkylgruppe, je mit 1 bis 12 Kohlenstoffatomen,
eine Alkenylgruppe oder eine Alkynylgruppe, je mit 3 oder 4 Kohlenstoffatomen, oder
eine Aralkylgruppe,
R³ ein Wasserstoffatom oder eine Methylgruppe,
R⁴ und R⁵ je eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen oder eine Cycloalkylgruppe
mit 5 bis 8 Kohlenstoffatomen,
X ein Sauerstoffatom oder eine NH-Gruppe,
Y ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen oder eine -C
nH
nCOOR⁷-Gruppe, in der n 0 oder eine ganze Zahl von 1 bis 10 ist und R⁷ ein Wasserstoffatom
ist, eine Alkylgruppe mit 1 bis 18 Kohlenstoffatomen, oder Y bedeutet einen Substituenten
der nachstehenden Formel:
in der:
R¹ und R² die gleiche Bedeutung wie oben haben, oder
Y ein Substituent der nachstehenden Formel ist:
in der:
R¹ und R² die gleiche Bedeutung wie oben haben, und R⁹ ein Wasserstoffatom oder eine
Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist,
m 1 oder 2 ist, und
p 0 oder 1 ist.
2. Eine Zusammensetzung elektrostatisch anziehbarer Tonerteilchen gemäß Anspruch 1, dadurch
gekennzeichnet, daß der farblose Ladungsregler in einem Gehalt zwischen 0,5 und 5
Gew.-% mit Bezug auf die gesamte Tonerzusammensetzung verwendet wird.
3. Eine Zusammensetzung elektrostatisch anziehbarer Tonerteilchen gemäß Anspruch 1 oder
2, dadurch gekennzeichnet, daß der farblose Ladungsregler aufgelöst oder dispergiert
ist in einem thermoplastischen Bindemittel, das ein Homo- oder Copolymeres von Styrol
ist, in dem der Styrolgehalt zumindest 50 Mol-% beträgt.
4. Eine Zusammensetzung elektrostatisch anziehbarer Tonerteilchen gemäß Anspruch 3, dadurch
gekennzeichnet, daß das Copolymere ein Styrol-Methylacrylat-Copolymeres, ein Styrol-Ethylacrylat-Copolymeres,
ein Styrol-n-Butylacrylat-Copolymeres, ein Styrol-n-Octylacrylat-Copolymeres, ein
Styrol-Methylmethacrylat-Copolymeres, ein Styrol-EthylmethacrylatCopolymeres, ein
Styrol-n-Butylmethacrylat-Copolymeres, ein Styrol-Isobutylmethacrylat-Copolymeres,
ein Styrol-n-Octylmethacrylat-Copolymeres, ein Styrol-Heptadecylmethacrylat-Copolymeres,
ein Styrol-ButadienCopolymeres oder ein Copolymeres von Styrol ist, das bis zu 25
Gew.-% Monomereinheiten, die eine Dialkylaminogruppe enthalten, enthält.
5. Eine Zusammensetzung elektrostatisch anziehbarer Tonerteilchen gemäß irgendwelchem
der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Farbstoff Gasruß ist.
6. Eine Zusammensetzung elektrostatisch anziehbarer Tonerteilchen gemäß irgendwelchem
der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Farbstoff ein organischer Farbstoff
oder ein organisches Pigment aus der Gruppe von Phthalocyaninfarbstoffen, Chinacridonfarbstoffen,
Triarylmethanfarbstoffen, Schwefelfarbstoffen, Acridinfarbstoffen, Azofarbstoffen
und Fluoreszeinfarbstoffen ist.
7. Eine Zusammensetzung elektrostatisch anziehbarer Tonerteilchen gemäß irgendwelchem
der vorstehenden Ansprüche, dadurch gekennzeichnet, daß sie weiter ein magnetisches
oder magnetisierbares Material umfaßt.
8. Eine Zusammensetzung elektrostatisch anziehbarer Tonerteilchen gemäß irgendwelchem
der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das basische Ringstickstoffatom
der Piperidingruppe in den Verbindungen gemäß der allgemeinen Formel (A) in Salzform
umgewandelt worden ist.
9. Eine Entwicklerzusammensetzung, die Tonerteilchen umfaßt, die der Zusammensetzung
gemäß irgendwelchem der vorstehenden Ansprüche entsprechen und mit Trägerteilchen
gemischt sind, die für den Gebrauch in der Kaskaden- oder Magnetbürstenentwicklung
latenter, elektrostatischer Ladungsbilder geeignet sind.
10. Eine Entwicklerzusammensetzung gemäß Anspruch 9, dadurch gekennzeichnet, daß die Trägerteilchen
zumindest dreimal größer sind als die Tonerteilchen und eine mittlere Korngröße zwischen
50 und 1000 µm haben.
11. Eine Entwicklerzusammensetzung gemäß Anspruch 9 oder 10, dadurch gekennzeichnet, daß
die Trägerteilchen aus mit einer Oxidschicht versehenem Eisen oder Stahl hergestellt
sind.
1. Une composition de particules de toner électrostatiquement attirables pour être utilisée
dans le développement d'images latentes électrostatiques, ces particules de toner
acquérant en présence de particules de support une charge positive grâce à une électrification
par contact triboélectrique, cette composition contenant comme liant une ou plusieurs
résines thermoplastiques en combinaison avec un colorant et un agent incolore contrôlant
les charges positives, caractérisé en ce que cet agent incolore contrôlant les charges
contient dans sa structure moléculaire au moins un groupe pipéridine substitué par
un groupe polyalkyle et un groupe phénole à empêchement stérique et qu'il a la formule
générale suivante (A):
dans laquelle:
R¹ représente un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone,
R² représente un groupe alkyle ou un groupe hydroxyalkyle ayant chacun 1 à 12 atomes
de carbone, un groupe alkényle ou un groupe alkynyle ayant chacun 3 ou 4 atomes de
carbone, ou un groupe aralkyle,
R³ représente un atome d'hydrogène ou un groupe méthyle,
R⁴ et R⁵ représentent chacun un groupe alkyle ayant 1 à 5 atomes de carbone ou un
groupe cycloalkyle ayant 5 à 8 atomes de carbone.
X représente un atome d'oxygène ou un groupe NH,
Y représente un atome d'hydrogène, un groupe alkyle ayant 1 à 12 atomes de carbone
ou un groupe -C
nH
nCOOR⁷, dans lequel n est 0 ou un nombre entier de 1 à 10 et R⁷ est un atome d'hydrogène,
un groupe alkyle ayant 1 à 18 atomes de carbone, ou Y représente un substituant de
la formule suivante:
dans laquelle:
R¹ et R² ont la même définition que ci-dessus, ou
Y est un substituant de la formule suivante:
dans laquelle
R¹ et R² ont la même définition que ci-dessus, et R⁹ est un atome d'hydrogène ou un
groupe alkyle ayant 1 à 4 atomes de carbone,
m est 1 ou 2, et
p est 0 ou 1.
2. Une composition de particules de toner électrostatiquement attirables selon la revendication
1, caractérisée en ce que l'agent incolore contrôlant les charges est utilisé dans
un taux entre 0,5 et 5 % en poids par rapport au total de la composition de toner.
3. Une composition de particules de toner électrostatiquement attirables selon la revendication
1 ou 2, caractérisée en ce que l'agent incolore contrôlant les charges est dissous
ou dispersé dans un liant thermoplastique qui est un homo- ou copolymère de styrène
dans lequel le taux de styrène est au moins 50 mol-%.
4. Une composition de particules de toner électrostatiquement attirables selon la revendication
3, caractérisée en ce que le copolymère est un copolymère de styrène et d'acrylate
de méthyle, un copolymère de styrène et d'acrylate d'éthyle, un copolymère de styrène
et d'acrylate de n-butyle, un copolymère de styrène et d'acrylate de n-octyle, un
copolymère de styrène et de méthacrylate de méthyle, un copolymère de styrène et de
méthacrylate d'éthyle, un copolymère de styrène et de méthacrylate de n-butyle, un
copolymère de styrène et de méthacrylate d'isobutyle, un copolymère de styrène et
de méthacrylate de n-octyle, un copolymère de styrène et de méthacrylate d'heptadécyle,
un copolymère de styrène et de butadiène ou un copolymère de styrène comprenant jusqu'à
25 % en poids d'unités monomères à groupe dialkylamino.
5. Une composition de particules de toner électrostatiquement attirables selon l'une
quelconque des revendications 1 à 4, caractérisée en ce que le colorant est du noir
de fumée.
6. Une composition de particules de toner électrostatiquement attirables selon l'une
quelconque des revendications 1 à 4, caractérisée en ce que le colorant est un colorant
ou un pigment organiques choisis parmi les colorants de phtalocyanine, les colorants
de quinacridone, les colorants de triarylméthane, les colorants de soufre, les colorants
d'acridine, les colorants azo et les colorants de fluorescéine.
7. Une composition de particules de toner électrostatiquement attirables selon l'une
quelconque des revendications précédentes, caractérisée en ce qu'elle comprend en
plus un matériau magnétique ou magnétisable.
8. Une composition de particules de toner électrostatiquement attirables selon l'une
quelconque des revendications précédentes, caractérisée en ce que l'atome d'azote
alcalin nucléaire du groupe pipéridine dans les composés selon la formule générale
(A) a été transformé sous forme de sel.
9. Une composition développatrice comprenant des particules de toner qui correspondent
à la composition selon l'une quelconque des revendications précédentes et qui sont
mélangées avec des particules de support appropriées à être utilisées dans le développement
en cascade ou à la brosse magnétique d'images latentes de charges électrostatiques.
10. Une composition développatrice selon la revendication 9, caractérisée en ce que les
particules de support sont au moins 3 fois plus grandes que les particules de toner
et qu'elles ont une granularité moyenne entre 50 et 1000 µm.
11. Une composition développatrice selon la revendication 9 ou 10, caractérisée en ce
que les particules de support sont faites de fer ou d'acier munis d'une couche d'oxyde.