U.S. patent number 3,650,797 [Application Number 05/037,472] was granted by the patent office on 1972-03-21 for developing electrostatic latent images with a mixture of positive and negative toners.
This patent grant is currently assigned to Kalle Aktiengesellschaft. Invention is credited to Martha Nee Kunitzer Tomanek.
United States Patent |
3,650,797 |
Tomanek |
March 21, 1972 |
DEVELOPING ELECTROSTATIC LATENT IMAGES WITH A MIXTURE OF POSITIVE
AND NEGATIVE TONERS
Abstract
This invention relates to a developer and process for developing
an electrostatic latent image, which process comprises applying to
the image, in the absence of a carrier, a mixture consisting of
effective amounts of at least one fusible, organic toner capable of
acquiring a positive charge, and at least one infusible, inorganic
toner of approximately the same effective particle size capable of
acquiring a negative charge. The developed image is fused by
heating and then treated with an alkaline liquid which removes the
inorganic toner particles and renders hydrophilic the image free
areas.
Inventors: |
Tomanek; Martha Nee Kunitzer
(Wiesbaden-Biebrich, DT) |
Assignee: |
Kalle Aktiengesellschaft
(Wiesbaden-Biebrick, DT)
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Family
ID: |
25983296 |
Appl.
No.: |
05/037,472 |
Filed: |
May 18, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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598152 |
Dec 1, 1966 |
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123099 |
Jul 11, 1961 |
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Foreign Application Priority Data
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Jul 27, 1960 [DT] |
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K 41304 |
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Current U.S.
Class: |
430/49.5;
101/463.1; 430/108.7; 430/109.3; 430/108.8; 430/108.1; 101/453;
427/375 |
Current CPC
Class: |
G03G
9/08 (20130101); G03G 13/28 (20130101) |
Current International
Class: |
G03G
13/28 (20060101); G03G 9/08 (20060101); G03g
013/08 (); G03g 013/22 () |
Field of
Search: |
;252/62.1 ;117/17.5
;96/1 ;101/455,463 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Cabic; Edward J.
Parent Case Text
This application is a continuation of Ser. No. 598,152, filed Dec.
1, 1966, and now abandoned, which is a continuation-in-part of my
copending application Ser. No. 123,099, filed July 11, 1961, and
now abandoned.
Claims
What is claimed is:
1. A process of developing an electrostatic latent image on a
supported photoconductive layer which comprises
applying to the image a mixture consisting of effective amounts of
at least one fusible, organic resinous toner capable of acquiring a
positive charge and at least one infusible, inorganic toner of
approximately the same effective particle size capable of acquiring
a negative charge, the two toners having opposite charges when in
admixture,
fusing the developed image by heating, and
treating the layer with an alkaline liquid, whereby the inorganic
toner particles are removed and the image-free areas of the
photoconductive layer are rendered hydrophilic.
2. A process according to claim 1 in which the layer having the
fused image thereon is treated with an organic alkaline liquid,
whereby the image-free areas of the layer are removed from the
support.
3. A process according to claim 1 in which the toners have an
average particle size in the range of about 1 to 50 .mu..
4. A process according to claim 1 in which about 1 to 20 parts by
weight of inorganic toner are present per part by weight of organic
toner.
5. A process according to claim 1 in which the organic toner
comprises a colored mixture of polystyrene and a maleinate
resin.
6. A process according to claim 1 in which the organic toner
comprises a colored ketone resin.
7. A process according to claim 1 in which a small quantity, in the
range of about 0.1 to 10 per cent by weight, of a compound selected
from the group consisting of waxes, aromatic compounds melting in
the range of about 40 to 150.degree. C., and substitution products
thereof, is added to the organic toner.
8. A process according to claim 1 in which the toners have an
average particle size in the range of 1 to 10 .mu..
9. A process according to claim 1 in which the toners have an
average particle size in the range of 10 to 20 .mu..
10. A process according to claim 1 in which the inorganic toner is
kieselguhr.
11. A process according to claim 1 in which the inorganic toner is
silica gel.
12. A process according to claim 1 in which the inorganic toner is
borax.
13. A process according to claim 1 in which the inorganic toner is
a mixture of kieselguhr and borax.
Description
The present invention relates to an electrophotographic developer
consisting of a mixture of toners, of about equal grain size and
carrying small charges of opposite polarity, which is capable of
uniformly developing even fairly large areas. In particular, the
present invention relates to a process for preparing offset
printing plates by electrophotographic means, using the
developer.
It is known to electrophotographically prepare images by a process
in which a photoconductor coating on a support is provided in the
dark with an electrostatic charge. Then, the material is exposed,
either by the contact process by illumination through a master or
by image projection using an optical apparatus, an electrostatic
image corresponding to the master being thus formed. This image is
developed by brief contact with a developer consisting of a toner
and a carrier, in the course of which the toner adheres to the
image portions. The image is then fixed, for example by heating or
by treatment with solvent vapor. In this way, copies are obtained
electrophotographically which are resistant to abrasion.
In the mixture of carrier and toner hitherto used for the
development of electrostatic latent images, particles were used for
the carrier which were ten to a hundred times larger and of greater
specific gravity then those used for the toner, e.g., grains with a
diameter of 0.2 to 0.6 mm. Because of their size, gravity acting on
the carrier particles is greater than the attraction of these
particles to the charged portions of the photoconductor coating so
that they do not adhere thereto.
Further, developer powders are known which consist of a mixture of
two toners of opposite charge which are of about the same size but
of different color. The developers of this type serve for
developing electrostatic images in various colors. In these
developers, both toners are fusible.
As toner, fine pigmented or non-pigmented thermoplastic or fusible
electroscopic resin powder has been used.
When the developer is moved about, the toner acquires a charge, as
a result of frictional electricity, which is the opposite of that
on the carrier. Therefore, the fine resin powder is loosely held by
the carrier material so that the two components do not become
dissociated. When the electrostatic image is powdered over with the
developer, the toner particles are drawn, in the case of opposite
polarity, to the image that is being developed and are held there,
while the carrier particles roll away. Thus, according to the
polarity of the toner contained in the developer, or that of the
electrostatic image, either the image portions or the image-free
portions of the electrophotographic material are covered on
development.
Latent electrostatic images also have been made visible by means of
finely divided resin powder contacted with the electrostatic image
by means of a current of air. With this method of development, a
relatively large number of particles are deposited on the
image-free portions and cause an undesirable "background."
The known developers all have the disadvantage that they do not
uniformly develop image portions covering rather large areas, but
are deposited only around the edges leaving the inside portions of
such areas to all intents and purposes undeveloped.
The present invention provides a developer for charge images which
uniformly adheres even to relatively large areas of the same charge
and yields a visible image of good marginal definition, which is
free of fog and undesirable edge effects. This is of particular
importance in the case of offset printing plates prepared by
electrophotographic means. In this case, it is an additional
requirement that the background, i.e., the image-free areas, be
clean and easily rendered hydrophilic.
The developer of the invention consists of a mixture of at least
one fusible organic resinous toner capable of acquiring a positive
charge and at least one infusible, inorganic toner capable of
acquiring a negative charge.
Organic materials suitable for the resinous positive toner of the
developer include natural and synthetic resins, e.g., colophony,
copals, dammar resin, asphalts, colophony modified phenol resins,
ketone resins, maleic resins, coumarone resin, polyacrylic acid
resin and polystyrenes. Mixtures of these resins also can be used.
Inorganic and/or organic pigments and/or dyestuffs are added to
these resins to give them a definite positive polarity. These
include, for example, carbon black, zinc oxide, titanium dioxide,
barium sulfate, red lead and the following dyestuffs from Schultz'
"Farbstofftabellen," Vol. I, 7th Edition (1931): Helio Red RMT (No.
200), Helio Fast Blue (No. 1188), Sudan dyestuffs, e.g., I (No.
33), II (No. 92), III (No. 532), CB (No. 127), R (No. 149),
Cellitone dyestuffs (Color Index, Vol. I, 2nd Edition, 1956, pages
1655-1742), Spirit-Soluble Nigrosine (No. 985), Pigment Black B
(No. 1361), Alizarin Blue Black B (No. 1195), Diamond Black F (No.
614), Fanal Violet LB (No. 803), and also mixtures of such
dyestuffs and/or pigments. Frequently, very small quantities of
these substances are sufficient, e.g., 0.5 percent of carbon black,
to give the resins definite positive character. It is also often
advantageous for small quantities, e.g., 0.1 to 10 per cent,
preferably 1 to 5 per cent, of waxes and/or low melting point
organic compounds and substitution products thereof, to be added to
the positive toners so that the melting point and the adherence of
the toner mixture is adjusted in the desired manner.
Waxes suitable for this purpose include natural waxes such as
carnauba wax, beeswax, Japan wax, montan wax and ceresine,
synthetic waxes such as those known under the denominations A Wax,
OP Wax, SPO Wax, V Wax, O Wax, E Wax, Hard Wax H and Hard Wax W,
various so-called "Ruhr" waxes, and in particular the products
marketed under the name "Gersthofener" waxes with the codings S, L,
O and OP, and waxlike substances such as hard paraffin, stearic
acid, high-pressure hydrated waxes and stearic alcohol.
As low-melting point organic compounds, substituted and
unsubstituted aromatic compounds with melting points between about
40 and 150.degree. C. are particularly of interest. Such compounds
are naphthols, e.g., 1-naphthol and 2-naphthol, and also aromatic
compounds such as acenaphthene, acylamino compounds such as
acetanilide, halogen aromatic compounds such as p-dibromobenzene,
amino compounds such as 2,4-diamino-toluene, o-phenylene diamine
and phenols such as resorcinol and diphenylamine and derivatives
thereof.
The positive toners are prepared as follows: The starting
materials, preferably in small pieces, are ground together very
finely, the mixture is heated to the melting point, the melt is
stirred until a high degree of homogeneity is attained, and it is
then cooled. Alternatively, the fusible starting materials may be
liquefied by heating and the remaining components then introduced
with stirring, after which the material is cooled. The toner mass
obtained in this way is then finely ground and sieved. For the
toner, fractions with an average grain size of about 1 to 50 .mu.,
preferably the fractions of about 1 to 10 .mu. or of about 10 to 20
.mu., are used. The fractions of smaller size are preferably used
for the reproduction of fine screens, while the coarser toners are
used for normal written text.
As the inorganic toner which acquires a negative charge, finely
pulverized inorganic substances such as salts, e.g., potassium
sulfate, calcium sulfate, ammonium chloride, sodium chloride,
potassium bromide, copper sulfate, aluminum/potassium sulfate and
sodium sulfate; oxides, e.g., ferric oxide, titanium dioxide, zinc
oxide, aluminum oxide, and copper oxide; silicates, e.g.,
kieselguhr, silica gel, talcum, and glass powder; borates, e.g.,
sodium metaborate, and potassium borate; carbonates, e.g., calcium
carbonate, magnesium carbonate, and potassium carbonate, may be
used.
The inorganic substances also are finely ground and sieved where
necessary; average grain sizes of about 1 to 50 .mu., preferably
about 1 to 10 .mu. or 10 to 20 .mu., are used. Mixtures of
different inorganic toners also may be used with advantage;
mixtures of kieselguhr and borax are preferred.
For the preparation of the developer, one or more of the inorganic
toners which acquire a negative charge and one or more of the
organic resinous toners which acquire a positive charge are mixed
together in the proportions of 1:1 to 20:1. About equal proportions
of the two types of toner are preferable.
The developers are applied to latent electrostatic images which are
to be developed in known manner and are then fixed, preferably by
heating.
The method by which the latent electrostatic image is produced is
immaterial, e.g., by the action of visible, ultraviolet, infra-red
or X-rays on layers of appropriate sensitivity, or by direct
electronic production of the image on an insulating layer, or by
the transfer of an electrostatic image to an insulating layer. It
is also possible for the permanent fixing of the toners on the
photoconductor coating to be carried out by the use of solvents for
the toners or for the photoconductor coating, particularly solvents
in vapor form. Also, the electrostatic image being developed can be
transferred, before fixing, to another material, particularly by
means of a corona discharge, and then fixed to the transfer
material.
The present invention also provides a process for preparing an
offset printing plate which comprises developing an electrostatic
latent image on a photoconductive layer with a mixture of at least
one fusible organic resinous toner capable of acquiring a positive
charge and at least one infusible, inorganic toner capable of
acquiring a negative charge, wherein both toners, which are of
approximately the same effective particle size, have an average
particle size in the range of about 1 to 50 .mu. and wherein 1 to
20 parts by weight of inorganic toner are present per part by
weight of organic toner, heating the developed powder image to a
temperature somewhat below the softening point of the layer to fuse
the organic toner, and treating the image with an alkaline liquid,
whereby the loosely adhering negative inorganic toner is removed
and the image-free areas are rendered hydrophilic.
The image-free areas of electrophotographic layers containing zinc
oxide as the photoconductive substance may be rendered hydrophilic
easily by means of aqueous alkaline solutions containing hexacyano
iron acid salts.
If the photoconductor coating is applied to a supporting material
which is suitable for electrophotographic purposes and satisfies
the requirements of planographic printing, i.e., has a hydrophilic
surface, the image-free portions, if they are aklali-soluble, can
be dissolved away completely in a subsequent operation by treatment
with an alkaline liquid, while the image portions carrying the
hydrophobic toner are inked up with greasy ink. A printing plate
prepared in this way is suitable for planographic printing. Organic
alkaline solvents are used as decoating liquids; liquid aliphatic
amines or amino alcohols admixed with mono- or polyhydric alcohols
are preferred.
Normally, the process according to the present invention is
performed as follows: A presensitized electrophotographic printing
plate consisting of an aluminum foil having a thin coating of an
organic photoconductor in an organic binder is charged in the usual
manner and then exposed. The latent electrophotographic image
formed is developed by drawing the foil through the developer
mixture of the present invention or by moving the mixture
repeatedly to and fro over the foil. The positive toner of the
developer adheres during this process to the negatively charged
portions of the image, and the negatively charged toner to the
uncharged portions. If fixing is then effected by heating, the
positive organic toner melts and becomes firmly anchored to the
coating. If the fixing temperature is below the melting and
softening point of the coating, the negative toner afterwards can
be removed since it has not become anchored to the layer. The most
favorable fusing temperature is best determined by tests. The
temperature selected should be such that the organic component on
the image areas melts uniformly and becomes anchored to the layer,
whereas the inorganic component does not stick to the layer. As a
rule, the most favorable temperature is in the range between 130
and 160.degree. C.
The toners have the advantage that, because of the small charges
they carry, they are capable of developing large areas and do not
adhere merely to the edges of the image. Moreover, letters become
sharper. Since the inorganic component surrounds the organic
component, the latter is prevented from running during the melting
process. In addition thereto, the inorganic component has a
cleaning effect which is particularly pronounced in the preparation
of printing plates where the plate is wiped with an alkaline
liquid. Since the inorganic toner adheres to the image-free areas,
those organic toner particles which normally cause a contamination
of the background areas deposit on the inorganic toner component.
When the plate is wiped over with the alkaline liquid, they are
removed together with the inorganic component, and thus can not be
fused to the image-free areas, as would be the case otherwise.
The invention will be further illustrated by reference to the
following specific examples:
EXAMPLE 1
Eight parts by weight of polyvinyl carbazole and 0.025 part by
weight of Rhodamine B extra are dissolved in 100 parts by volume of
toluene; this solution is applied in known manner to a paper and
then dried. The electrocopying material thus prepared is negatively
charged by a corona discharge and then exposed by the contact
process, by illumination through a positive master. Development is
then effected with a developer consisting of 10 parts by weight of
kieselguhr and 10 parts by weight of a pigmented resin mixture. For
the preparation of the pigmented toner, 30 parts by weight of a
polystyrene of low melting point ("Polystyrol" LG), 30 parts by
weight of a maleinate resin e.g., "Hobimal" P 59), and six parts by
weight of Pigment Red B are melted together. After cooling, the
melt is ground and sieved. The fraction of a particle size of about
10 .mu. is mixed with kieselguhr in equal proportions. When this
developer is scattered on the latent electrostatic image, the
red-pigmented, positively charged toner is attracted by the
negative charge image so that a visible red image is formed and the
colorless negative toner (kieselguhr) is repelled. The latter
adheres to the uncharged parts of the electrocopying material. The
toner image is fixed by heating to about 130.degree. C. Very sharp
copies with large colored areas are obtained.
EXAMPLE 2
An aluminum plate upon which selenium has been vacuum-deposited is
positively charged by a corona discharge of 6,000 volts and then
illuminated through a negative master. The electrostatic image
produced is powdered over with a developer consisting of 50 parts
by weight of finely ground silica gel of an average particle size
of 10 to 20 .mu. and 25 parts by weight of a toner made up of 20
parts by weight of a maleinate resin ("Beckacite K 105"), 10 parts
by weight of polystyrene, four parts by weight of carbon black and
two parts by weight of Pigment Black. These substances are melted
together and, after cooling, the melt is ground and sieved and the
fraction of a particle size of 10-20 .mu. is used. The positive
pigmented toner is repelled by the positively charged portions and
is deposited on the uncharged portions. A positive image becomes
visible; the image that has been made visible can be transferred to
any supporting material, e.g., paper, aluminum or plastic. Images
rich in contrast with large black areas are obtained.
EXAMPLE 3
A foil made of bright, rolled aluminum that has been cleaned with
trichloroethylene, is coated with a mixture of 30 parts by volume
of ethylene glycol monomethylether, one part by weight of
2,5-bis-(4'-diethylaminophenyl-1')-1,3,4-oxadiazole and 0.8 part by
weight of a styrene/maleic anhydride interpolymer with a specific
gravity of 1.26-1.28 and a decomposition temperature ranging from
200 to 240.degree. C.; it is then dried. For the production of
images on the electrocopying material thus obtained, the coating is
negatively charged by a corona discharge and then illuminated
through a positive master with a 125-watt high pressure mercury
vapor lamp for one second. The electrostatic image of the master
thereby produced is treated with a mixture consisting of 10 parts
by weight of borax and three parts by weight of the positive toner
described in Example 2. The two toners have a particle size of
about 10 .mu.. When this developer is distributed on the
electrostatic image, the black-pigmented positive toner is
attracted to the negative charge image and the colorless negative
toner is repelled. The latter therefore adheres to the uncharged
parts of the electrocopying coating. The toner image is fixed by
heating to about 160.degree. C. Images rich in contrast are
obtained, in which extensive black areas are also evenly
developed.
EXAMPLE 4
The procedure described in Example 3 is followed but, for
development, a toner mixture is used which consists of 20 parts by
weight of purified kieselguhr and 10 parts by weight of a ketone
resin (AP resin) pigmented with carbon black and spirit-soluble
nigrosine. The purification of the kieselguhr is effected in the
following manner: 20 parts by weight of a commercial product are
first boiled for one hour with 300 parts by volume of 15 per cent
hydrochloric acid. After cooling, the material is filtered, washed
with water, and dried. The product is then heated to glowing (about
600-800.degree. C.). The kieselguhr purified in this manner, in
association with the pigmented toner, gives especially uniformly
developed areas.
After the electrophotographic image has been fixed by heating to
140.degree. C., it can be converted into a printing plate if the
image-free portions, and the kieselguhr adherent thereto, are wiped
over with a solution consisting of 10 per cent mono-ethanolamine, 5
per cent of sodium silicate, 20 per cent of glycerine, 10 per cent
of triglycol, and 55 per cent of methanol. After a brief rinsing
with water, the plate can be inked up with greasy ink and used for
printing in an offset machine.
EXAMPLE 5
A foil made of brushed aluminum is coated with a mixture of 100
parts by volume of glycol monomethyl ether, four parts by weight of
2,5-bis-(4'-diethylaminophenyl-(1') )-1,3,4-triazole, four parts by
weight of a maleinate resin with an acid number of 110-130 (e.g.,
"Alresat" 400 C), and 0.001 part by weight of Crystal Violet; it is
then dried. For the production of images on the electrocopying
material thus obtained, the coating is negatively charged with a
corona discharge, exposed beneath a positive master to a 100-watt
incandescent lamp for two seconds, and the latent electrostatic
image of the master thus produced is treated with a mixture
consisting of 10 parts by weight of kieselguhr, 10 parts by weight
of borax, and eight parts by weight of the positive toner described
in Example 2. The powders have a particle size of about 10-20 .mu..
When this developer is distributed on the electrostatic image, the
pigmented positive toner is attracted by the negative charge image
and the mixture of inorganic toners is repelled. The latter
therefore adhere to the uncharged margins of the black image and,
after the image has been fixed by heating to 160.degree. C., they
can be wiped away with a cotton pad. Images rich in contrast with
good full tones are obtained.
It will be obvious to those skilled in the art that many
modifications may be made within the scope of the present invention
without departing from the spirit thereof, and the invention
includes all such modifications.
* * * * *