U.S. patent number 3,615,404 [Application Number 04/724,224] was granted by the patent office on 1971-10-26 for 1,3-phenylenediamine containing photoconductive materials.
This patent grant is currently assigned to The Scott Paper Company. Invention is credited to John Alan Mattor, Lawrence Price.
United States Patent |
3,615,404 |
Price , et al. |
October 26, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
1,3-PHENYLENEDIAMINE CONTAINING PHOTOCONDUCTIVE MATERIALS
Abstract
A new group of N,N,N',N'-substituted-1,3-phenylenediamines and
an electrophotographic material comprised of a slightly conductive
support and an insulating coating thereon comprised of an
insulating resin, and a N,N,N',N'-substituted-1,3-phenylenediamine
photoconductor. An electron-acceptor sensitizing agent can also be
added to the insulating coating.
Inventors: |
Price; Lawrence (N/A),
Mattor; John Alan (N/A, ME) |
Assignee: |
Company; The Scott Paper
(PA)
|
Family
ID: |
24909549 |
Appl.
No.: |
04/724,224 |
Filed: |
April 25, 1968 |
Current U.S.
Class: |
430/74; 430/73;
564/384; 564/391; 252/501.1; 430/83; 564/386; 564/431 |
Current CPC
Class: |
G03G
5/0614 (20130101) |
Current International
Class: |
G03G
5/06 (20060101); G03G 005/06 () |
Field of
Search: |
;252/501 ;96/1.5,1.6
;260/576 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lesmes; George F.
Assistant Examiner: Cooper; John C.
Claims
We claim:
1. An electrophotographic material comprising a relatively more
conductive support having a photoconductive insulating layer
thereon which comprises a photoconductor selected from the class
consisting of N,N'-di-o-xylylene-1,3-phenylenediamine and
substituted 1,3-phenylenediamines having the general formula:
##SPC6##
wherein R is a divalent arylene group selected from the class
consisting of 1,3-phenylene; 4-methyl-1-3,phenylene;
4-ethyl-1,3-phenylene; 4-halo-1,3phenylene;
4-isopropylene-1,3-phenylene;4-methoxy-1,3phenylene;
2-halo-1,3-phenylene; and 4,6-dimethyl-1,3-phenylene; R' is a
divalent arylene group selected from the class consisting of
1,3-phenylene; 4-methyl-1,3-phenylene; 4-ethyl-1,3-phenylene and
4-isopropyl-1,3-phenylene; Z is an aralkyl group selected from the
class consisting of benzyl, monomethylbenzyl, dimethylbenzyl,
trimethylbenzyl, monohalobenzyl and dihalobenzyl; and "alkyl"
represents an alkyl group containing from one to six carbon
atoms.
2. An electrophotographic material as claimed in claim 1 wherein
the insulating layer contains an electron-acceptor sensitizing
agent.
3. An electrophotographic material as claimed in claim 2 wherein
the photoconductive insulating layer comprises a photoconductor
having the general formula ##SPC7##
wherein R is a divalent arylene group selected from the class
consisting of 1,3-phenylene, 4-methyl-1,3-phenylene,
4-ethyl-1,3-phenylene, 4-halo-1,3-phenylene,
4-isopropyl-1,3-phenylene, 4-methyloxy-1,3-phenylene,
2-halo-1,3-phenylene and 4,6-dimethyl-1,3-phenylene and Z is an
aralkyl group selected from the class consisting of benzyl,
monomethylbenzyl, dimethylbenzyl, trimethylbenzyl,
tetramethylbenzyl, monohalobenzyl and dihalobenzyl.
4. An electrophotographic material as claimed in claim 3 wherein
the photoconductive insulating layer comprises a photoconductor
having the general formula ##SPC8##
wherein R is a divalent arylene group selected from the class
consisting of 1,3-phenylene, 4-methyl-1,3-phenylene,
4-ethyl-1,3-phenylene, 4-halo-1,3-phenylene,
4-isopropyl-1,3-phenylene, 4-methyoxy-1,3-phenylene,
2-halo-1,3-phenylene and 4,6-dimethyl-1,3-phenylene; Z is an
aralkyl group selected from the class consisting of benzyl,
monomethylbenzyl, dimethylbenzyl, trimethylbenzyl, and
tetramethylbenzyl, monohalobenzyl and dihalobenzyl; and Z' is a
dissimilar aralkyl group selected from the group designated by
Z.
5. An electrophotographic material as claimed in claim 2 wherein
the photoconductive insulating layer comprises a photoconductor
having the general formula ##SPC9##
wherein R' is a divalent arylene group selected from the class
consisting of 1,3-phenylene, 4-methyl-1,3-phenylene,
4-ethyl-1,3-phenylene and 4-isopropyl-1,3-phenylene; Z is an aralky
group selected from the class consisting of benzyl,
monomethylbenzyl, dimethylbenzyl, trimethylbenzyl,
tetramethylbenzyl, monohalobenzyl and dihalobenzyl; and "alkyl"
represents an alkyl group containing from one to six carbon
atoms.
6. An electrophotographic material as claimed in claim 2 wherein
the electron acceptor is 9,10-phenanthrenedione.
7. An electrophotographic material as claimed in claim 3 wherein
the photoconductor is N,N,N',N'-tetrabenzyl-1,3-phenylenediamine
and the electron acceptor is 9,10-phenanthrenedione.
8. An electrophotographic material as claimed in claim 2 wherein
the electron acceptor is 9-fluorenone, 2,4,7-trinitrofluorenone, or
2-nitrofluorenone.
9. An electrophotographic material as claimed in claim 3 wherein
the photoconductor is
N,N,N',N'-tetra-(4-methylbenzyl)-1,3-phenylenediamine or
N,N,N',N'-tetra(2,5-dimethylbenzyl)-1,3-phenylenediamine.
10. An electrophotographic material as claimed in claim 2 wherein
the electron acceptor is 2,4,3'-trinitrostilbene,
2,4-dinitrostilbene or 2,4,6-trinitrostilbene.
Description
BACKGROUND OF THE INVENTION
This invention relates to photographic reproduction and more
particularly to a new group of organic photoconductors and to
electrophotographic processes, namely processes in which an
electrostatic latent image is produced by utilizing the property of
photoconduction (i.e., a variable conductivity dependent on the
intensity of illumination). The electrostatic latent image may be
produced in a conventional exposure operation, for example by means
of a lens-projected image or by contact-printing techniques,
whereby a nonvisible electrostatic charge pattern (the so-called
electrostatic latent image) is created on a surface, in which
pattern the charge density at any point is related to the intensity
of illumination obtained at the point during the exposure. The
latent image may be developed (i.e., rendered visible) by means of
a triboelectric powder or liquid toner. Said powder, such as a
pigmented synthetic resin, fixes the resulting visible image by
rendering the powder permanently adherent to a support on which the
image is desired, for example in suitable cases by heating to
soften or melt the powder particles. The liquid toner particles
which are washed over the surface are caused to adhere permanently
by the drying oil component of the liquid toner.
In electrophotographic processes the electrostatic latent image is
commonly formed on the surface of a photoconductive insulating
layer carried on a support. For example, material comprising such
support and photoconductive layer may be charged by applying a
uniform surface charge to the free surface of the photoconductive
layer. The charge can be applied by conventional means such as
corona discharge or the like. The charge is retained due to the
substantial insulating character, i.e., the low conductivity, of
the insulating layer in the dark. On exposure as described above,
the photoconductive property of the layer causes the conductivity
to increase in the illuminated areas to an extent which is
proportional to the intensity of illumination. This results in a
leakage of the surface charge in the illuminated areas while the
charge in the unilluminated areas remains. This is what constitutes
the aforementioned charge pattern or electrostatic latent
image.
Electrophotographic processes have become of increasing importance
in recent years, especially in connection with office duplicating
processes. Consequently, there has been much interest aroused and
much effort has been made to obtain suitable materials for making
the support and photoconductive insulating layers used in such
copying processes.
Attempts have been made to develop colorless organic
photoconductors; however, problems have been encountered in
obtaining colorless photoconductors sufficiently sensitive to be
imaged using known light sources without being so sensitive as to
become severely discolored by the interaction of light and oxygen
during aging.
It is therefore the major objective of the present invention to
provide a new group of colorless organic photoconductors that do
not become appreciably discolored when exposed to light and oxygen.
The invention is also directed to a new electrophotographic
material which is quickly and easily imaged by exposure to commonly
employed light sources.
PRIOR ART
In recent years many investigations have been made with respect to
the nature of suitable photoconductive materials. Most notable
among the photoconductive substances hitherto used in
electrophotographic processes have been inorganic materials such as
zinc oxide and selenium.
However, within the last few years the search for suitable
photoconductors has been broadened to include organic chemical
compounds and polymers. As a result of these searches several
classes of organic compounds have been found to be useful as
photoconductors; included in this group are the 2,5 bis
(p-aminophenyl)-1,3,4-oxadiazoles, U.S. Pat. No. 3,189,447;
2-aryl-4-arylidene oxazolones, U.S. Pat. No. 3,072,479; substituted
Schiff bases, U.S. Pat. No. 3,041,165; aryl-substituted-p
and-m-phenylenediamines, U.S. Pat. Nos. 3,314,788, 3,141,770, and
3,265,496; N-disubstituted benzylideneazines, U.S. Pat. No.
3,290,147, and various other compounds, see Great Britain, Pat. No.
895,001.
U.S. Pat. No. 3,314,788 describes the use of
N,N,N',N'-tetrabenzyl-p-phenylenediamines and
N,N'-dibenzyl-N,N'-dialkyl substituted-p-phenylenediamines as
organic photoconductors. While electrophotographic plates or sheets
having coatings containing the substituted-p-phenylenediamines give
good prints, it has been discovered that they discolor appreciably
upon aging in the presence of light and oxygen. Upon exposure to
light in the presence of oxygen the p-phenylenediamines cause the
sheet to turn dark yellow or brown, thus making the
electrophotographic product containing them unsuitable for use when
it must be exposed to light for any period of time. However, the
N,N,N',N'-substituted-1,3-phenylenediamines of the present
invention have been found to be very stable and do not discolor
appreciably when exposed to light and oxygen for substantial
periods of time. Thus electrophotographic sheets or plates having a
coating containing the substituted-1,3-phenylenediamines of the
present invention can be exposed to light and oxygen for long
periods of time without the coatings turning dark yellow or
brown.
SUMMARY OF THE INVENTION
a. New N,N,N',N'-substituted-1,3-phenylenediamines.
The new N,N,N',N'-substituted-1,3-phenylenediamine compounds of the
present invention correspond to one of the ##SPC1##
In the present specification and claims, R represents
1,3-phenylene, 4-methyl-1,3-phenylene, 4-halo-1,3-phenylene,
4-ethyl-1,3-phenylene, 4-isopropyl-1,3-phenylene,
4-methoxy-1,3-phenylene, 2-halo-1,3-phenylene and
4,6-dimethyl-1,3-phenylene and Z represents benzyl,
monomethylbenzyl, dimethylbenzyl, trimethylbenzyl,
tetramethylbenzyl, monohalobenzyl or dihalobenzyl; however, when R
represents 1,3-phenylene, Z must represent monomethylbenzyl,
dimethylbenzyl, trimethylbenzyl, tetramethylbenzyl, monohalobenzyl,
or dihalobenzyl; Z' represents a dissimilar moiety selected from
the group designated by Z, and R' represents 1,3-phenylene,
methyl-1,3-phenylene, 4-ethyl-1,3-phenylene, or
4-isopropyl-1,3-phenylene. The terms "alkyl" and "halo" as employed
in the present specification and claims represent an alkyl moiety
having from one to six carbon atoms, inclusive, and a halogen
selected from the group consisting of bromine or chlorine. The new
N,N,N',N'-tetrabenzyl-1,3-phenylenediamines and
N,N'-dialkyl-N,N'-dibenzyl-1,3-phenylenediamines of the present
invention are hereinafter referred to as substituted
1,3-phenylenediamines for the sake of convenience. These new
substituted 1,3-phenylenediamines are oils, noncrystalline solids
or crystalline solids which are soluble in various common organic
liquids and substantially insoluble in water.
The new N,N,N',N'-tetrabenzyl-1,3-phenylenediamines of the present
invention corresponding to the formula ##SPC2##
are prepared by reacting a 1,3-phenylenediamine corresponding to
the formula H.sub.2 N-R-NH.sub.2 with a benzyl halide corresponding
to the formula Z-X, where X represents bromine or chlorine. The
reaction between the 1,3-phenylenediamine and benzyl halide takes
place readily in an inert organic solvent as reaction medium and at
temperatures within the range of from 40.degree. to 150.degree. C.
with the production of the desired substituted 1,3-phenylenediamine
product and the hydrogen halide of reaction. The temperature of the
reaction mixture is maintained within the reaction temperature
range for from 1 to 4 hours and conveniently until there is a
substantial cessation in the production of the hydrogen halide of
reaction.
The proportions of the reactants to be employed are not critical,
some of the desired product being produced when the reactants are
contacted together in any proportions. The reaction consumes 4
molar proportions of a benzyl halide such as benzyl chloride or
benzyl bromide for each molar proportion of 1,3-phenylenediamine;
however, in a preferred procedure the benzyl halide is employed in
an amount slightly in excess (about 10 percent) of the
stoichiometric amount necessary to react with all of the
1,3-phenylenediamine. The use of a larger excess of the benzyl
halide does not adversely affect the yield or the desired
product.
In carrying out the reaction, the benzyl halide and
1,3-phenylenediamine are dispersed in the inert organic reaction
medium in any order or fashion. Representative inert organic
liquids include ethanol, methyl cellosolve, 2-propanol, and
methanol. It is preferred that the solvents be at least slightly
polar in nature. Following the addition of the reactants to the
reaction medium the resulting reaction mixture is heated at a
temperature within the reaction temperature range. In a convenient
procedure, the reaction mixture is heated at the reflux temperature
of the reaction mixture. In order to obtain optimum yields, a base
such as sodium hydroxide or potassium hydroxide is added to the
reaction mixture in order to neutralize the reaction mixture and
prevent the formation of the hydrohalide salt of the
1,3-phenylenediamine starting material. In a convenient procedure,
the temperature of the reaction mixture is maintained within the
reaction temperature range until there is a substantial cessation
in the production of hydrogen halide byproduct as indicated by the
amount of base, preferably an aqueous base, needed to neutralize
the reaction mixture.
The water added to the reaction mixture with the aqueous base can
be removed by azeotropic distillation with additional inert organic
solvent being added to the reaction mixture to replace the solvent
lost during the distillation. However, it is not necessary to
remove the water from the reaction mixture as the product separates
during the reaction period as an oil and can be easily isolated
from the reaction mixture.
Following the reaction period, the desired product can be isolated
from the reaction mixture by conventional procedures. In a
convenient procedure, the oily product is separated by decantation
and thereafter dissolved in an organic solvent such as acetone. The
solvent solution is filtered to remove the salt byproduct formed
during the neutralization procedure and cooled. During the cooling
procedure, the product separates as an oil, noncrystalline solid,
or crystalline solid. This product can then be further purified by
such conventional procedures as washing, crystallization,
distillation or recrystallization.
Mixed symmetrical substituted 1,3-phenylenediamines corresponding
to the formula ##SPC3##
wherein Z is as previously described and Z' represents a dissimilar
radical selected from the group comprising Z, are prepared by
reacting an N,N'-disubstituted-1,3-phenylenediamine corresponding
to the formula
Z-HN-R-NH-Z
with a benzyl halide corresponding to the formula Z'-X, wherein Z'
represents a moiety from the group designated by Z which is
different from the Z substituent on the N,N'-1,3-phenylenediamine.
The N,N'-disubstituted-1,3-phenylenediamine starting material is
prepared by the condensation of 1,3-phenylenediamine with the
appropriate benzyl alcohol (Z-OH) according to the method of Y.
Sprinzac, J. Am. Chem. Soc., 78, 3207(1956). The reaction between
the N,N'-disubstituted-1,3-phenylenediamine and benzyl halide takes
place in an inert organic solvent as the reaction medium and occurs
readily at temperatures of from 40.degree. to 150.degree. C. and
preferably at the boiling temperature of the reaction mixture.
While the proportions of the reactants to be employed are not
critical, optimum yields are obtained by employing the benzyl
halide in an amount slightly in excess (about 10 percent) of the
stoichiometric amount necessary to react with the
N,N'-disubstituted-1,3-phenylenediamine. The reaction is carried
out and the product isolated in the same manner as described for
the other N,N,N',N'-tetrabenzyl-1,3-phenylenediamine products of
the present invention.
The group of new N,N'-dialkyl-N,N'-dibenzyl-1,3-phenylenediamine
compounds corresponding to the formula ##SPC4##
are prepared by reacting together N,N'-dialkyl-1,3-phenylenediamine
and a benzyl halide corresponding to the formula Z-X, dispersed in
an inert organic solvent such as ethanol, methyl cellosolve, or
2-propanol as reaction medium. The reaction proceeds readily at
temperatures from 40.degree. to 150.degree. C., with the
temperature of the reaction mixture being maintained within the
reaction temperature range for from about 1 to 4 hours. During the
reaction period, the reaction mixture is neutralized by the
addition of aqueous base as previously described. Following the
reaction period the desired product is isolated from the reaction
mixture and further purified using the same procedures as
previously described for the production of the
N,N,N',N'-tetrabenzyl-1,3-phenylenediamines.
In a preferred procedure,
N,N'-diethyl-N,N'-dibenzyl-1,3-phenylenediamine is prepared by
ethylation of the appropriate N,N'-dibenzyl-1,3-phenylenediamine
corresponding to the formula
Z-HN-R'-NH-Z.
The ethylation is carried out in an excess of the ethylating agent
as reaction medium. Representative ethylating agents include
triethylphosphate and diethyl sulfate.
In carrying out the reaction, the reactants are contacted together
at temperatures of from 150.degree. to 250.degree. C. for from 1 to
4 hours. However, in a convenient procedure, the reaction mixture
is maintained at the reflux temperature for from 1 to 4 hours.
Following the reaction period, the reaction mixture is treated with
an aqueous base to hydrolyze the polyphosphates formed during the
reaction period and to facilitate the isolation of the desired
product. During the hydrolysis procedure, the desired product
separates in the reaction mixture as an oily residue which is then
extracted from the reaction mixture with ether. The ether extract
is then dried and fractionally distilled to obtain the desired
product.
As previously stated the new substituted-1,3-phenylenediamine
products of the present invention are oils, noncrystalline solids
or crystalline solids. It has been found that when seed crystals
for the oils and noncrystalline materials are obtained, the oils
and noncrystalline products can be caused to readily crystallize.
The oils and noncrystalline solids are conveniently prepared for
use as photoconductors as follows: the oil or noncrystalline solid
is dissolved in an organic solvent and the solvent solution washed
with water to remove any salt remaining in the product. In those
cases where it is found that the product does not form a
crystalline solid the reaction mixture is diluted with water to
remove ionic materials. The recovered oil is then washed with an
alcohol such as methanol or ethanol. The washed oil is then
dissolved in chloroform and the chloroform solution dried,
filtered, stripped of low boiling constituents to yield the product
as an oily residue. This residue can then be dissolved in an
organic solvent and employed as a photoconductor as described in
the present specification and claims.
Representative benzyl halides to be employed as starting materials
for the production of the substituted 1,3-phenylenediamines include
4-chlorobenzyl chloride, 4-methylbenzyl chloride,
2,5-dimethylbenzyl chloride, 4-bromobenzyl bromide,
2,3,5,6-tetramethylbenzyl bromide, 2,3,4,5-tetramethylbenzyl
chloride, 2-chlorobenzyl chloride, 3,4-dichlorobenzyl chloride,
3,5-dibromobenzyl bromide and 3-chlorobenzyl chloride.
b. Electrophotographic Material.
The new electrophotographic material of the present invention is
comprised of a conductive support layer, being coated on at least
one surface thereof with a photoconductive insulating layer, said
photoconductive insulating layer being comprised of an insulating
resin binder, and a substituted 1,3-phenylenediamine or
N,N,N',N'-tetrabenzyl-1,3-phenylenediamine.
The substituted 1,3-phenylenediamines correspond to ##SPC5##
N,n,n',n'-tetrabenzyl-1,3-phenylenediamine and
N,N'-di-o-xylylene-1,3,-phenylenediamine have been found to be
useful as organic photoconductors. The new substituted
1,3-phenylenediamines, N,N'-di-o-xylylene-1,3-phenylenediamine and
N,N,N',N'-tetrabenzyl-1,3-phenylenediamine will be referred to as
TSMPD for the sake of convenience. The TSMPD compounds generally
absorb the lower end of the ultraviolet spectrum (i.e., 3300 A. and
below). Therefore, when it is desired to shift the spectral
response of the electrophotographic product of the present
invention to a longer wavelength, an electron-accepting sensitizing
agent is added to the TSMPD-containing photoconductive layer. The
sensitizer compounds serve as electron acceptors, and in addition
to shifting the spectral response, these sensitizers facilitate
mobile charge carrier transport, thereby increasing the efficiency
of the system. Representative sensitizers are the substituted
fluorene compounds such as 9-fluorenone,
2,4,7-trinitro-9-fluorenone and 2-nitrofluorene; and substituted
stilbenes such as 2,4,3'-trinitrostilbene, 2,4-dinitrostilbene, and
2,4,6-trinitrostilbene and substituted benzothiazoles such as
2-styrylbenzothiazole, 3-nitrophenylbenzothiazole,
2-phenylbenzothiazole, 2-(3'-nitrophenyl)-benzothiazole,
2-(4'-dimethylamino)-benzothiazole,
4-phenylbutadienyl-2-benzothiazole, 2-styrylquinoline,
p-nitroacetophenone, 1,1-dicyano-4-phenylbutadiene,
9,10-phenanthrenedione, 3,5-dinitromethyl benzoate,
2,4-dinitrophenyl sulfide, 2,4,4'-trinitrodiphenyl ether,
bis(3-nitrophenyl) disulfide bis(4-chloro-2-nitrophenyl) disulfide,
and cyanine dyes, such as Orthochrome T, pinacyanol, Kryptacyanine,
and ethyl red.
In preparing the photoconductive insulating layers the TSMPD
compounds and the sensitizer, if utilized, are employed in
association with a resin or synthetic polymer, for example: natural
resins, synthetic resins (including copolymers) such as the
polystyrenes or polystyrene copolymers including styrene-butadiene,
styrene-butadiene-acrylonitrile; acrylates, polyvinyl acetals,
polycarbonates, polyphenylene oxide, phenoxy resins, polysulfones,
polyesters and other synthetic polymeric resinous materials.
The TSMPD photoconductive substances and sensitizers when used for
preparation of the photoconductive insulating layer are preferably
so used in solution in organic solvents, such as for example
ethanol, benzene, chloroform, acetone, toluene, methylene chloride,
methyl ethyl ketone or ethylene glycol monomethyl ether. Mixtures
of two or more TSMPD compounds may be employed. Mixtures of
solvents may also be used. It is also possible to employ the
photoconductive substances in association with other organic
photoconductive substances.
In producing the electrophotographic plate or sheet material of the
present invention the TSMPD compound or mixture thereof is employed
in an amount equivalent to from 0.01 to 200 or more percent by
weight with respect to the resinous binder. In many cases the
photoconductive TSMPD compound or mixture thereof may be employed
at greater than 200 percent with advantageous results. The amount
of TSMPD to be employed will depend upon the system in which the
product is being utilized, i.e. the particularly light source, the
length of exposure, the particular TSMPD compound being used,
etc.
The amount of electron-acceptor sensitizing agent to be utilized
will vary depending upon such factors as the sensitizer, the TSMPD,
the light source and the length of exposure. The TSMPD compounds of
the present invention can be employed without the use of a
sensitizer at 3600 A. or below. However, it is generally desirable
to employ a sensitizer to shift the spectral response. In such
cases the amount employed will be within the range of from 0.01 to
20 percent by weight of the TSMPD compound.
The support may be of any material suitable for use in
electrophotographic processes, for example, aluminum or other metal
plates or foils, plastic foil and preferably paper sheets or webs.
When paper is to be used as a support for the photoconductive
layer, it is preferable that it shall have been pretreated against
penetration by the coating solution, for example with
methyl-cellulose in aqueous solution; polyvinyl alcohol in aqueous
solution; a solution in acetone and methyl ethyl ketone of a mixed
polymer of acrylic acid methyl ester and acrylonitrile; or with
solutions of polyamides in aqueous alcohols or a coating containing
some conductive polymer such as polyvinylbenzyltrimethylammonium
chloride. Solutions of the photoconductive substances and
insulating resins in organic solvents are applied to the support by
known methods (for example, by spraying, reverse-roll coating, or
whirl coating). Following the coating procedure, the coating thus
prepared is dried.
The photoconductive layers are usually charged positively or
negatively by means of a corona discharge. The light sensitivity of
the thus obtained photoconductive layers lies mainly in the range
of 3,000 to 7,000 A. Very good images may be obtained by a short
exposure using a positive or negative to a conventional
electrophotographic light source such as a high-pressure mercury
vapor lamp, tungsten lamp or the like.
The latent image so produced may be developed in known fashion by
the application of dry powder or liquid toner.
The following examples are merely illustrative and are not deemed
to be limiting.
PREFERRED EMBODIMENTS
Example 1.
Meta-phenylenediamine (10.8 grams, 0.1 mole) and benzylchloride
(50.6 grams, 0.4 mole) were dispersed in 70 ml. of methyl
cellosolve. The reaction mixture thus prepared was then heated at
the reflux temperature. Within a few minutes the acid salt began to
precipitate in few reaction mixture. This acid salt was neutralized
by the periodic addition of an aqueous sodium hydroxide (20 grams,
0.5 mole in 20 ml. of water). The refluxing of the reaction mixture
was continued throughout the addition of the aqueous base. The
water so added was removed by azeotropic distillation, with
additional methyl cellosolve added to the reaction mixture slowly
portionwise. After refluxing for one hour, 0.1 mole of benzyl
chloride was added to the reaction mixture and the refluxing
continued for an additional hour. Following the reaction period,
the reaction period, the reaction mixture was filtered while hot to
remove the precipitated sodium chloride, and the filtrate
recovered. The filtrate was allowed to cool whereupon an oily
product began to separate. Acetone was added to the filtrate to
keep the oily product in solution. The filtrate was then cooled in
an ice bath and seed crystals were added to initiate the
crystallization of the desired product. The solid product was
isolated by filtration and recrystallized from a solution of equal
parts of acetone and ethanol. The recrystallized
N,N,N',N'-tetrabenzyl-1,3-phenylenediamine was found to melt at
99-100.degree. C.
In a similar manner, the following products of the invention are
prepared by reacting 1,3-phenylenediamine with the appropriate
substituted benzyl chloride corresponding to the formula Z-Cl:
N,N,N',N'-tetra-(2-methylbenzyl)-1,3-phenylenediamine
(m.p.164.degree.-166.degree. C.)
N,N,N',N'-tetra-(4-methylbenzyl)-1,3-phenylenediamine
(m.p.101.degree.-103.degree. C.)
N,N,N',N'-tetra-(2-chlorobenzyl)-1,3-phenylenediamine (m.p.
173.degree.-175.degree. C.).
N,N,N',N'-tetra-(4-chlorobenzyl)-1,3-phenylenediamine
(m.p.133.degree.-135.degree. C.)
N,N,N',N'-tetra-(2,5-dimethylbenzyl)-1,3-phenylenediamine
(m.p.164.degree.-167.degree. C.)
N,N,N',N'-tetra-(3,4-dichlorobenzyl)-1,3phenylenediamine
(m.p.126.degree.-128 .degree. C.)
N,N,N',N'-tetra-(3-methylbenzyl)-1,3-phenylenediamine (oil)
N,N,N',N'-tetra-(3,4-dimethylbenzyl)-1,3-phenylenediamine (oil)
N,N,N',N'-tetra-(2,3,5,6-tetramethylbenzyl)-1,3-phenylenediamine
(m.p.129.degree.-149.degree. C.)
N,N,N',N'-tetra-(2,4,6-trimethylbenzyl)-1,3-phenylenediamine
(m.p.183.degree.-193.degree. C.).
In other similar procedures, the following new compounds of the
present invention are prepared by reacting (a)
4-methyl-1,3-phenylenediamine; or (b)
4-chloro-1,3-phenylenediamine; or (c)
4-isopropyl-1,3-phenylenediamine; or (d)
4-methoxy-1,3-phenylenediamine; or (e)
2-chloro-1,3-phenylenediamine; or (f)
4,5-dimenthyl-1,3-phenylenediamine with the appropriate substituted
benzyl chloride.
a. N,N,N',N'-tetrabenzyl-4-methyl-1,3-phenylenediamine
(m.p.94.degree.-97.degree. C.)
N,N,N',N'-tetra-(2-methylbenzyl)-4-methyl-1,3-phenylenediamine
(m.p.117.degree.-119.degree. C.)
N,N,N',N'-tetra-(4-chlorobenzyl)-4methyl-1,3-phenylenediamine (m.p.
110.degree.-111.degree. C.)
N,N,N',N'-tetra-(2,5-dimethylbenzyl)-4-methyl-1,3-phenylenediamine
(m.p. 158.degree.160.degree. C.)
b. N,N,N',N'-tetrabenzyl-(4-chloro-1,3-phenylenediamine) (m.p.
107.5.degree.-109.5.degree. C.)
N,N,N',N'-tetra-(2-methylbenzyl)-4-chloro-1,3-phenylenediamine
(m.p. 129.degree.-132.degree. C.)
N,N,N',N'-tetra-(2,5-dimethylbenzyl)-4-chloro-1,3-phenylenediamine
(m.p. 158.degree.-160.degree. C.)
c. N,N,N',N'-tetrabenzyl-(4-isopropyl-1,3-phenylenediamine)
(m.p.112.degree.-114.degree. C.)
N,N,N',N'-tetra-(2-chlorobenzyl)-4-isopropyl-1,3-phenylenediamine
(m.p. 134.degree.-137.degree. C.)
N,N,N',N'-tetra-(4-methylbenzyl)-4-isopropyl-1,3-phenylenediamine
(oil)
d. N,N,N',N'-tetrabenzyl-(4-methoxy-1,3-phenylenediamine) (m.p.
115.degree.-117.degree. C.)
e. N,N,N',N'-tetrabenzyl-(2-chloro-1,3-phenylenediamine) (m.p.
106.degree.-108.degree. C.)
f. N,N,N',N'-tetrabenzyl-(4,5-dimethyl-1,3-phenylenediamine)
(oil)
Example 2.
N,N'-diisopropyl-1,3-phenylenediamine (4grams, 0.0021 mole) and
2,5-dimethylbenzyl chloride (7.16 grams, 0.0046 mole) were
dispersed in 20 milliliters of ethanol. The reaction mixture thus
prepared was heated at the reflux temperature for 1.5 hours. During
the reflux period the reaction mixture was periodically neutralized
by the addition of aqueous sodium hydroxide. Following the reaction
period, the reaction mixture was filtered while hot and the
filtrate cooled. The oily product which separated from the filtrate
was washed with water and ethanol. The oily product was then
dissolved in chloroform, dried over sodium sulfate, and distilled
under reduced pressure to remove the low-boiling constituents and
obtain the
N,N'-diisopropyl-N,N'-di-(2,5-dimethylbenzyl)-1,3-phenylenediamine
product as an oil.
In further operations, using the procedure set forth in the
previous paragraph the following compounds of the present invention
are prepared:
N,N'-di-sec.-butyl-N,N'-dibenzyl-1,3-phenylenediamine (oil) by
reacting together N,N'-di-sec.-butyl-1,3-phenylenediamine and
benzyl chloride.
N,N'-di-sec.-butyl-N,N'-di(2-chlorobenzyl) phenylenediamine (an
oil) by reacting together N,N'-di-sec.-butyl-1,3-phenylenediamine
and 2-chlorobenzyl chloride.
N,N'-diisopropyl-N,N'-dibenzyl-1,3-phenylenediamine (an oil) by
reacting together N,N'-diisopropyl-1,3-phenylenediamine and benzyl
chloride.
Example 3.
N,N'-dicyclohexyl-1,3-phenylenediamine (10 grams, 0.037 mole) and
2,5-dimethylbenzyl chloride (15.5 grams, 0.1 mole) were dispersed
in 25 milliliters of methyl cellosolve and the reaction mixture
thus prepared heated at the reflux temperature for 2 hours. During
the reflux period, aqueous sodium hydroxide (4 grams in 7
milliliters of water) was added periodically to neutralize the
reaction mixture. Following the reflux period, 10 milliters of
methyl cellosolve was added to the reaction mixture and the mixture
filtered while hot. The filtrate thus obtained was allowed to cool
whereupon the N,N'-dicyclohexyl-1,3-phenylenediamine product
separated as an oil. This oily product was collected by
decantation, washed with ethanol and water and dissolved in
chloroform. This chloroform solution was evaporated to dryness to
obtain the
N,N'-dicyclohexyl-N,N'-di-(2,5-dimethylbenzyl-1,3-phenylenediamine
product as a glassy noncrystalline solid.
In a similar procedure, the
N,N'-dibenzyl-N,N'-dicyclohexyl-1,3-phenylenediamine (oil) was
prepared by reacting N,N'-dicyclohexyl-1,3-phenylenediamine with
benzyl chloride.
Example 4.
n,n'-dibenzyl-1,3-phenylenediamine (10 grams, 0.035 mole) and
2,5-dimethylbenzyl chloride (12.5 grams, 0.08 mole) were dispersed
in 50 milliliters of isopropanol and the resulting mixture heated
at the reflux temperature for 2.5 hours. Aqueous potassium
hydroxide was periodically added to the reaction mixture. Following
the reflux period the oil which separated in the reaction mixture
during the reflux period was taken up in hot acetone and the hot
acetone solution was filtered. The filtrate was then allowed to
cool, whereupon the
N,N'-dibenzyl-N,N'-di-(2,5-dimethylbenzyl)-1,3-phenylenediamine
product precipitated as a crystalline solid. This solid product was
recrystallized from an acetone-ethanol mixture and the
recrystallized product found to melt at 124.degree.-126.degree.
C.
Example 5.
N,N'-dibenzyl-1,3-phenylenediamine (25 grams, 0.087 mole) and
triethyl phosphate (15.9 grams, 0.087 mole) were placed in a
reaction vessel and heated until the exothermic reaction started,
whereupon the heat was removed. The reaction was allowed to proceed
for about 10 minutes and then -phenylenediamine was heated at the
reflux temperature for about 50 minutes. Following the reflux
period, aqueous sodium hydroxide (12 grams NaOH in 50 ml. of water)
was added to the reaction mixture and the mixture thereafter heated
for 1 hour. During the heating period an oily product separated in
the aqueous mixture. Following this heating period the aqueous
mixture and oily product were allowed to cool. The oily product was
then extracted with diethyl ether, the ether layer washed with
water, dried over sodium sulfate and fractionally distilled. The
N,N'-diethyl-N,N'-dibenzyl-1,3-phenylenediamine product distilled
over at 225.degree.-235.degree. C. at 0.1 mm. of mercury.
Example 6.
A photoconductive insulating coating was prepared by mixing
Toluene 11 .9 liters Polystyrene (Dow Chemical Co. 2 .3 kilograms
styron 666u) N,N,N',N'-tetrabenzyl-1,3- 1 0.6 kilogram
phenylenediamine 9,10-phenanthrenedione 4grams (dissolved in 200
milliliters of chloroform)
The above-listed constituents were thoroughly mixed to provide a
uniform coating composition. This coating composition was applied
by means of a reverse-coil coater to one side of a 34-pound paper
base stock having on each side thereof a 10-pound base coating of
clay, titanium dioxide, polyvinyl alcohol and electrically
conductive polyvinyl benzyl trimethyl ammonium chloride. The
photoconductive insulating coating was applied in an amount
equivalent to 5 pounds dry weight of coating per ream (25 inches X
38 inches--500 sheets). This paper yielded a clear image upon
exposure using 200-watt high-pressure mercury light source
(microfilm projection exposure) for 5 seconds. The imaged paper was
very stable showing barely discernable discoloration after 30
minutes in a Fade-ometer Microfilm projection exposures were
effected using silver, Kalvar and diazo microfilms.
In another operation, a photoconductive coating varying from the
above described coating only by having 4 grams of
2,4,3'-trinitrostilbene in place of the 9,10-phenanthrenedione was
prepared and coated on the same body stock. This paper yielded a
clear image which did not discolor appreciably when placed in the
Fade-ometer for 30 minutes.
Example 7.
N,N,N',N'-tetra-(2-methylbenzyl)-1,3-phenylenediamine (0.25 grams),
tetramethylthiuram disulfide, toner set, (0.07 grams) and
2-styrylbenzothiazole (0.03 gram) were dissolved in 20 grams of a
polymer solution comprised of polystyrene (Dow Chemical Company,
Styron 666U) dissolved in 108 milliliters of chloroform. The
coating composition was mixed thoroughly and thereafter applied to
a paper base sheet by means of a No. 20 Meyer bar. The coating was
then dried, charged by means of a corona discharge and imaged
through a transparency by means of a high-pressure mercury vapor
lamp for a period of 10 seconds. The imaged surface was then
treated with a standard, commercial liquid toner. A sample of the
paper thus produced was placed in the Fade-ometer for 30 minutes
with only very slight discoloration.
Example 8.
A coating composition is prepared by mixing 1 part by weight of
N,N,N',N'-tetra-(4-methylbenzyl)-1,3-phenylenediamine, 3 parts by
weight of polysulfone P-4700 (manufactured by the Union Carbide
Corporation), 0.0005 part by weight of 2,4,3'-trinitrostilbene, and
15 parts by weight of toluene as a solvent. This coating
composition is applied to a suitable paper substrate which has been
base-coated with 8 pounds (dry weight) per ream (25 inches X 38
inches--500 sheets) of a coating comprised of 70 parts by weight of
polyvinyl alcohol, 20 parts by weight of calcium carbonate and 10
parts by weight of polyvinyl benzyl trimethyl ammonium
chloride.
A positive print is made by negatively charging the coated paper by
means of a corona discharge, and subsequently exposing the paper
sheet through a positive transparency to a high-pressure mercury
light source at 22 cm. for 4 seconds.
The latent electrostatic image thus produced is developed by
applying thereto a dry, positively charged thermoplastic resinous
toner (comprising carbon black particles coated with thermoplastic
resin). The toner thus applied is attracted to the latent image
areas producing a visible image which is permanently fixed by
heating the thermoplastic toner on the sheet surface at a
temperature of 100.degree.--130.degree. C for short time which
solidly fuses the toner.
The clear print thus prepared shows no appreciable discoloration
when placed in a Fade-ometer for 30 minutes. developing produced
the positively
In another variation of the procedures of this example, all steps
are repeated as described above except that the coated paper is
positively charged, and the developing toner is negatively charged.
Clear images are produced when the positively charged paper is
developed with the negative toner.
It is a unique characteristic of the coatings of the present
invention that in addition to the clear images obtained by
oppositely charged electrophotographic sheets and toner, excellent
results may be obtained by employing sheets and toner having like
charges. Thus, positively charged paper and positive toner may be
employed in one variation, and negatively charged paper and
negative toner in yet another. Both of these like charged
combinations produce clear, sharp images with no appreciable
discoloration in light and oxygen for substantial periods of
time.
Example 9.
In another example, a coating composition is prepared by mixing 2
parts by weight of tetrabenzyl-1,3-phenylenediamine, 3 parts by
weight of polyvinyl butyral (Butvar B-76, manufactured by the
Monsanto Chemical Company) as a resinous binder, 0.002 parts by
weight of a sensitizing dye (ethyl red), and 15 parts by weight of
a solvent for the above composition, which solvent component is
comprised of 9 parts by weight of toluene and 6 parts by weight of
methyl ethyl ketone.
This coating composition is applied to one side of a web of
bleached paper bodystock having a basis weight of 40 pounds per
ream, and previously coated with 8 pounds (dry weight) per ream of
the base coating described in Example 8.
The paper sheet thus coated is negatively charged by means of a
corona discharge, and charged sheet is then exposed through a
positive transparency to a 60-watt tungsten lamp at a distance of
22 cm. for 15 seconds.
The latent image thus produced in selected areas of the copy sheet
is developed by applying to the exposed surface a positively
charged liquid toner comprised of an oxidizing oil which has been
intimately admixed with a colored body (carbon black), this
composition having been dispersed in a strongly insulating liquid
(deodorized kerosene). The particles of oil and carbon black are
attracted to the laten image areas in the exposed sheet, and a
clear, sharp visible image is produced. No heat-fusing step is
necessary in this method as the oil quickly hardens and adheres
permanently upon exposure to air.
The thus produced is placed in a Fade-ometer for 60 minutes with
only very slight discoloration.
Example 10.
The various TSMPD compounds and sensitizers listed below were made
into coating compositions by dissolving 0.5 gram of the TSMPD and
1.5 grams of polystyrene in 12 milliliters of chloroform. In the
resulting solution the sensitizer was dissolved in a quantity
expressed as percent weight based on the weight of TSMPD present.
In each case the solution was spread on a paper base sheet by means
of a No. 20 Meyer bar, about 3 to 4 pounds dry weight per ream,
being applied.
---------------------------------------------------------------------------
Amount of TSMPD Compounds Sensitizer Sensitizer in % of TSMPD
N,N,N',N'-tetra(2,5-dimethyl benzyl)-4-methyl-1,3-phenylenediamine
2-styrylbenzothiazole 2%
N,N,N',N'-tetrabenzyl-4-isopropyl-1,3-phenylenediamine
2-styrylkenzothiazole 2%
N,N,N',N'-tetrabenzyl-4-methoxy-1,3-phenylenediamine
2-styrylbenzothiazole 2%
N,N'-dicyclohexyl-N,N'-dibenzyl-1,3-phenylenediamine
9,10-phenanthrenedione 0.5
N,N'-diethyl-N,N'-dibenzyl-1,3-phenylenediamine
9,10-phenanthrenedione 0.5
N,N,N',N'-tetrabenzyl-1,3-phenylenediamine 2,4-dinitrostilbene 1
N,N,N',N'-tetrabenzyl-1,3-phenylenediamine 2-strylbenzothiazole 1
N,N'-dibenzyl-N,N'-(2,5dimethyl benzyl)-1,3-phenylenediamine
9,10-phenanthrenedione 0.5
N,N,N',N'-tetra(3,4-dichloro-benzyl)-1,3-phenylenediamine
2-styrylbenzothiazole 2 N,N,N',N'-tetra(2-methyl
benzyl)-1,3-phenylenediamine 2-styrylbenzothiazole 2
N,N,N',N'-tetra(4-chloro-benzyl)-4-methyl-1,3-phenylenediamine
2-styrylbenzothiazole 2
__________________________________________________________________________
Each of these sheets was charged negatively by a corona discharge,
imaged through a positive transparency by means of ultraviolet
light for 5 seconds. The image was then developed with a positive
liquid toner. All sheets gave a clean well-defined image which did
not discolor appreciably when placed in a Fade-ometer for 30
minutes.
Example 11.
In further operations a photoconductive coating was prepared by
combining N,N,N',N'-tetra-(2,5-dimethylbenzyl)-1,3-phenylenediamine
(0.5 gram), polyvinyl butyral (21.5 grams of a solution comprised
of 12 grams of polymer in 108 ml. chloroform) and
2-(-4-diethylaminobenzylidene)-picoline methiodide. The coating
thus prepared was applied to the base stock described in example 6
by means of a No. 20 Meyer bar. The sheet was charged to 800 volts
and showed little dark decay and retained 15 volts after 10 seconds
of exposure to visible light. No discoloration was observed after
15 minutes in the Fade-ometer.
The Fade-ometer employed to test the electrophotographic materials
of the present invention is an Atlas Color Fade-ometer, Type FDA-R
sold by Atlas Electric Devices Company.
The starting 1,3-phenylenediamine and benzyl halide starting
materials employed in the present invention are all produced in
accordance with procedures well known in the art.
The N,N'-dialkyl-1,3-phenylenediamine starting materials are
prepared by a modification of the Jones and Cowie method (German
Pat. No. 927,165). The modified procedure comprises reacting a
ketone such as acetone, methyl ethyl ketone, cyclohexanone and the
like with a 1,3-phenylenediamine in the presence of platinum oxide
as a catalyst. The reaction is carried out for 8 hours in an excess
of the ketone as reaction medium in a high-pressure reactor at a
temperature of 160.degree. C. and under hydrogen at a pressure of
300 pounds per square inch.
Example12.
1,3-phenylenediamine (2.80 grams, 0.26 mole) and .alpha.,.alpha.'
dichloro-o-xylene (10 grams, 0.057 mole) were dispersed with
stirring in 40 milliliters of methyl cellosolve. The reaction
mixture was heated at 90.degree. C. for 1 hour. During the heating
period aqueous sodium hydroxide was periodically added to the
reaction mixture. The product precipitated as a crystalline solid
in the reaction mixture during the heating period. The reaction
mixture was filtered and the filter cake washed with water to
remove the salts, and remaining solid product was recrystallized
from chloroform-ethanol mixture. The recrystallized
N,N'-di-o-xylylene-1,3-phenylenediamine product was found to melt
at 232.degree.-235.degree. C.
* * * * *