U.S. patent number 3,624,226 [Application Number 05/017,932] was granted by the patent office on 1971-11-30 for electrographic organic photoconductor comprising of n,n,n',n', tetrabenzyl 4,4'oxydianaline.
This patent grant is currently assigned to Calgon Corporation. Invention is credited to Merwin Frederick Hoover, Dallas L. Schiegg.
United States Patent |
3,624,226 |
Hoover , et al. |
November 30, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
ELECTROGRAPHIC ORGANIC PHOTOCONDUCTOR COMPRISING OF N,N,N',N',
TETRABENZYL 4,4'OXYDIANALINE
Abstract
The present invention relates to the composition of N,N,N', N,'
tetrabenzyl 4,4' oxydianaline represented by the formula ##SPC1##
And its use as an organic photoconductor for preparing
photoconductive layers.
Inventors: |
Hoover; Merwin Frederick
(Pittsburgh, PA), Schiegg; Dallas L. (Pittsburgh, PA) |
Assignee: |
Calgon Corporation (Pittsburgh,
PA)
|
Family
ID: |
21785343 |
Appl.
No.: |
05/017,932 |
Filed: |
March 9, 1970 |
Current U.S.
Class: |
430/73; 564/386;
430/74; 564/391 |
Current CPC
Class: |
G03G
5/0618 (20130101) |
Current International
Class: |
G03G
5/06 (20060101); G03g 005/06 () |
Field of
Search: |
;96/1.5,1.6,1PC ;252/501
;260/612,576 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Litvinenko et al., Investigation of the Positive Bridging Effect in
Binuclear Ammines, J. Organic Chem. (USSR), V. 2, No. 10, pp.
1857-1864, Oct. 1966..
|
Primary Examiner: Van Horn; Charles E.
Claims
We claim:
1. An improved photoconductive layer comprising a high dielectric
resinous binder and a photoconductive compound wherein the
improvement comprises N,N,N',N' tetrabenzyl 4,4' oxydianaline as
the photoconductive compound.
2. An improved photoconductive layer as in claim 1 further
including a sensitizer.
3. An improved electrophotographic element comprising a
photoconductive layer coated onto a conductive support wherein the
improvement comprises N,N,N',N' tetrabenzyl 4,4' oxydianaline as
the photoconductive compound of the photoconductive layer.
4. An improved process of electrophotographic reproduction
comprising (a) charging an electrographic element comprising a
photoconductive layer coated onto a conductive support, (b)
exposing the element to a light image to produce an invisible
charge pattern, and (c) developing the invisible charge pattern
with an electrostatically charged toner wherein the improvement
comprises N,N,N',N' tetrabenzyl 4,4' oxydianaline as the
photoconductive compound of the photoconductive layer.
Description
BACKGROUND OF THE INVENTION
The present invention is directed to electrographics and,
particularly, it is directed to a novel organic photoconductor and
its use in preparing photoconductive elements for use in
electrographic imaging processes. More specifically, this invention
is directed to the novel composition of N,N,N',N' tetrabenzyl 4,4'
oxydianaline and its use as a photoconductor.
The term electrophotography, as generally understood in the art,
means a reproduction or copying process which utilizes a
combination of the electrostatics and the photoconductive phenomena
of substances. Electrophotographic processes which depend on
photoconductive layers are well known in the art. The most widely
used processes are xerography, which employs a selenium coated drum
as the photoconductive element, and "Electrofax," which uses zinc
oxide as the photoconductor. However, many other
photoconductographic processes are well known and reported in the
literature.
In an electrophotographic process the electrophotographic element
consists essentially of a layer of the photoconductive compound
coated on a relatively more conductive support such as
electroconductive paper, aluminum foil and the like. When in use,
the photoconductive layer is electrically charged in the dark with
a corona discharge or the like so that the coating has a uniform
positive or negative charge density on its surface. The element is
then exposed to a light image which activates the photoconductive
compound and an invisible charge pattern is developed on the
element. The invisible charge image is subsequently developed with
an electrostatically charged toner as is known by those in the
art.
In recent years much research has been expended trying to develop
suitable photoconductive materials. In the past, most
photoconductive layers used in the electrophotographic processes
have been based on the use of such inorganic materials as selenium,
zinc oxide, cadmium sulfide and the like as the photosensitive
element. However, much time has been spent investigating organic
photoconductors. Most notable among the organic photoconductors
which have heretofore been used are anthracene, anthraquinone,
carbazole and perylene. Recently much work has been done on the use
of organic photoconductors such as polyvinylcarbazole, N,N,N',N'
tetrasubstituted-p-phenylenediamines, and the disubstituted
benzylideneazines and the like. For example, see U.S. Pat. No.
3,421,891 which is directed to polyvinylcarbazoles and U.S. Pat.
No. 3,314,788 directed to the use of the N,N,N',N'
tetrasubstituted-p-phenylenediamines (TSPD) and U.S. Pat. No.
3,290,147 directed to the use of the N-disubstituted
benzylideneazines.
However, many of these organic photoconductors suffer from various
drawbacks. For instance, some of the compounds are not as
photosensitive as desired. Another serious drawback which is
especially associated with the TSPD compounds is their limited
solubility. The solubility of these compounds in the systems
preferred by the industry is very limited and the compounds tend to
crystallize rather than form a uniform coating. Therefore, it is an
object of this invention to provide a novel organic photoconductive
compound which is useful in preparing photoconductive elements.
SUMMARY OF THE INVENTION
We have found that N,N,N',N' tetrabenzyl 4,4' oxydianaline
##SPC2##
is a good photoconductor compound and is very useful in preparing
photoconductive elements. Our novel photoconductor is compatible
with most of the common resin binders systems used in preparing
electrophotographic plates. Moreover, our novel compound is also
readily soluble in most of the common solvents preferred by the
industry.
We do not wish to be bound by any theories but we believe that the
ether functional group enhances the utility of our compound. First,
the unshared electrons on the ether oxygen atom improve the
photoconductivity of our compound. In addition, the presence of the
ether oxygen also modifies the solubility properties. For example,
our compound is soluble in solvents such Tetrabenzyl cyclohexanone
and the like whereas the TSPD type compounds are not as readily
soluble. Our compound is therefore an improvement over the prior
art compounds.
We have prepared the N,N,N',N' tetrabenzyl 4,4' oxydianaline of out
invention in the following manner:
EXAMPLE 1
Preparation of N,N,N',N' Tetrabanzyl 4,4' Oxydianaline
Into a four-necked, one-liter flask equipped with a mechanical
stirrer, reflux condenser, thermometer and addition funnel was
charged 0.2 moles of 4,4' oxydianaline dissolved in 300 ml. of
Fischer's Reagent Alcohol (ethanol denatured with methanol and
isopropanol). Then 0.8 moles of benzyl chloride was added to the
reaction flask and the mixture brought to reflux temperature. Then
0.8 moles of potassium hydroxide dissolved in 150 ml. of reagent
alcohol was added dropwise over a period of one-half hour. After
the potassium hydroxide addition was completed, the reaction
mixture was refluxed for 1 hour. The reaction mixture was poured
into 1,000 ml. of hot water to dissolve the potassium chloride
which had precipitated. The resultant mixture was filtered and the
precipitate washed several times with hot water. The precipitate
was dissolved in chloroform and decolorized with Nuchar activated
carbon. The tetrabenzyloxydianaline was crystallized from the
chloroform solution by the addition of reagent alcohol. The result
was a 74 percent yield of N,N,N',N' tetrabenzyl 4,4' oxydianaline
which had a melting point of 114.degree. to 118.degree. C.
EXAMPLE 2
Preparation of N,N,N',N' Tetrabenzyl 4,4' Oxydianaline
Into a four-necked, one-liter flask equipped with a mechanical
stirrer, reflux condenser and thermometer was charged the following
reaction mixture: (a) 20 grams (0.1 moles) of purified 4,4'
oxydianaline; (b) 50.4 grams (0.4 moles) of benzyl chloride; (c)
33.6 grams (0.4 moles) sodium bicarbonate; (d) a solvent system
comprised of 300 ml. of ethanol and 100 ml. of distilled water. The
reaction mixture was brought to reflux temperature and refluxed for
about 5 hours. The reflux was discontinued when no more CO.sub.2
evolved from the reaction mixture. The reaction mixture was then
cooled and the heavy oily phase was dissolved in chloroform,
filtered and charcoal treated. The tetrabenzyloxydianaline was
crystallized from the chloroform solution by the addition of
reagent alcohol. The result was 45.4 grams (80 percent yield) of
N,N,N',N' tetrabenzyl 4,4' oxydianaline which had a melting point
of 114.degree. to 118.degree. C. The product obtained from this
procedure was considerably less colored and crystallized more
readily than the product obtained in example 1.
The novel photoconductor of our invention was evaluated in the
following manner. The tetrabenzyl oxydianaline (TBODA) was
formulated with a solvent and binder and then filmed onto a sheet
of aluminum foil. The TBODA film was charged with a high voltage
corona in the dark and the charge acceptance measured. The charged
film was then exposed to an ultraviolet light source and the charge
dissipation measured and recorded. The formulation used consisted
of 15 grams of polystyrene resin (Kopper's KTPL-7), 5 grams of the
TBODA and 100 grams of chloroform. The insensitized photoconductive
formulation was filmed onto filmed foil, air dried and then dark
adapted for 24 hours prior to evaluation. The charge acceptance
value (C.A.) was measured by placing an electrode on the charged
film immediately after discontinuing the corona. The ultraviolet
light source was turned on after the charge acceptance was
measured. The residual charge (R.C.) was measured by the voltage
level 15 seconds after the ultraviolet source was activated. The
light source used was an U.V. fluorescent apparatus with a peak
output at 3,660 A. The results of this test illustrated that TBODA
had photoconductive properties. The above experiment was repeated
using different known photoconductors in place of the TBODA. The
other photoconductors which were evaluated using this procedure
were N,N,N',N' tetrabenzyl paraphenylenediamine (TBPDA), and zinc
oxide. A comparison of the results as shown in table I clearly
illustrated that TBODA was a good photoconductor.
TABLE I
Compound Charge Acceptance (Volts) Residual Charge (Volts)
__________________________________________________________________________
TBPDA 400 150 ZnO* 600 0 TBODA 400 200
---------------------------------------------------------------------------
*a commercial "Electrofax" sheet with sensitizers included.
In addition to the above described evaluation, TBODA photoconductor
was evaluated by way of an actual electrophotographic printing
process. The TBODA photoconductor was formulated into a resin
binder system comprising of 10 grams of a polystrene resin
(Kopper's KTPL-7), 100 ml. of chloroform, and 5 grams of the TBODA
photoconductor. An electrophotographic plate was then prepared by
coating a conductive substrate with the TBODA formulation using a
number 40 draw rod. The conductive substrate was on aluminum foil,
polyethylene, paper laminate (Thilmany Paper Co. -83600). Prior to
coating, the aluminum foil laminated substrate was roughed up with
steel wool and scrubbed with chloroform. The resulting
electroconductive plate was dark conditioned for 24 hours before
using. The print was then made by taping the photoconductive plate
onto a grounded base and subjecting the plate to a 5.0 K.V.
positive corona for 30 seconds. An IRE facsimile test chart
photographic transparency was then quickly placed on the charged
plate and the plate then exposed for 5 seconds to ultraviolet light
from the fluorescent source. The latent charged image was then
developed by dusting the sheets with a mixture of Bruning type D
toner mixed with iron filings and removing the excess iron and
toner with a magnet. The plate was then permanentized by placing in
a 105.degree. C. oven for about 90 seconds. The quality of the
print was rated as fair. This rating was a subjective rating and
was assigned by paying particular attention to contrast,
resolution, and cleanliness of background. Two additional
electrophotographic plates were prepared and tested in the same
manner using the TBODA formulation which had been enhanced by the
incorporation of 0.005 grams of a sensitizer. The two sensitizers
which were utilized are 1-chloroanthraquinone and 2-methyl
anthraquinone. The quality of the print obtained from the
sensitized plates was rated as good. Both sensitized plates
produced reproductions that had good contrast and resolution and a
very clean background. In addition, electrophotographic plates were
prepared and tested in the same manner using a sensitized TBPDA
formulation in place of the TBODA. A comparison of the
reproductions clearly showed that TBODA was equal to or slightly
superior to TBPDA.
The electrophotographic elements of this invention are comprised of
an electrically conductive support which carries a photoconductive
layer. The photoconductive layer consists essentially of suitable
high dielectric film forming resinous binder which contains at
least about 10 percent by weight of TBODA. In addition, the
photoconductive layer may optionally contain a sensitizer.
The TBODA compound of our invention is also compatible with other
clear resinous dielectric binders in addition to polystyrene. It
may be used with other natural or synthetic polymeric binders such
as polyvinyl chloride, polyvinyl acetate, polyvinyl ether,
styrene-butadiene copolymers, polyvinylidene chloride, polyamides,
polyacrylates and methacrylates, phenol-formaldehyde resins,
paraffin, mineral waxes and the like. In addition, the binder
system may optionally contain a plasticizer as is recognized by one
skilled in the art. The plasticizer may be used to improve the film
strength and film forming ability of the photoconductive layer of
the electrophotographic element.
The TBODA compound is also readily soluble in such solvents as
chloroform, toluene, methyl ethyl ketone, acetone, cyclohexanone
and tetrahydrofuran.
The sensitizer constituent used in our invention may be either of
the dye sensitizer type or the chemical sensitizer type or a
combination of both types. The chemical type sensitizer is simply a
chemical compound which increases the photosensitivity of the
photoconductor. Many different theories have been advanced to
explain the mechanism of chemical sensitization, but generally
speaking, aromatic quinones and cyano compounds have been found to
increase the photosensitivity of photoconductors. Some examples of
these types of compounds are tetracyanoethylene,
tetracyanoquinone-dimethane (TCNQ), anthraquinone and the
substituted anthraquinones such as 2-methyl anthraquinone,
1-chloroanthraquinone, 1-nitroanthraquinone and the like. A dye
type sensitizer is a compound which increases the sensitivity of
the photoconductive compound by increasing or shifting the
wavelength range to which the photoconductor is photosensitive.
Examples of dye sensitizers are crystal violet, methylene blue,
rhodamine B, rose bengal and the like.
* * * * *