U.S. patent number RE28,698 [Application Number 05/495,520] was granted by the patent office on 1976-01-27 for electrophotographic material containing sensitizers.
This patent grant is currently assigned to Matsushita Electric Industrial Co., Ltd.. Invention is credited to Yo Hasegawa, Kazuhisa Morimoto, Yoshinobu Murakami.
United States Patent |
RE28,698 |
Murakami , et al. |
January 27, 1976 |
Electrophotographic material containing sensitizers
Abstract
An electrophotographic material is provided herein which
comprises a conductive support layer and a photoconductive
insulating layer, the latter layer comprising a photoconductive
polymeric compound such as poly-N-vinylcarbazole, and a sensitizer
having the following general formula ##SPC1## Wherein B represents
a radical selected from the group consisting of ##SPC2## ##SPC3##
Compounds falling under the latter general formula include such
compounds as 2-phenyl-4-[(2'-phenyl-4'-benzopyranylidene)
benzyl]-benzopyrylium perchlorate and 2,3-phenyl-4-[(2'-phenyl
4'-benzopyranylidene)benzyl]-6-methylbenzopyrylium perchlorate.
Inventors: |
Murakami; Yoshinobu
(Higashi-Osaka, JA), Hasegawa; Yo (Suita,
JA), Morimoto; Kazuhisa (Settsu, JA) |
Assignee: |
Matsushita Electric Industrial Co.,
Ltd. (Osaka, JA)
|
Family
ID: |
27457633 |
Appl.
No.: |
05/495,520 |
Filed: |
August 7, 1974 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
121508 |
Mar 5, 1971 |
03712811 |
Jan 23, 1973 |
|
|
Foreign Application Priority Data
|
|
|
|
|
Mar 13, 1970 [JA] |
|
|
45-21766 |
Mar 13, 1970 [JA] |
|
|
45-21767 |
|
Current U.S.
Class: |
430/71; 430/80;
549/388; 549/23; 549/213; 549/398; 430/83; 549/406; 549/212 |
Current CPC
Class: |
G03G
5/067 (20130101); G03G 5/0674 (20130101) |
Current International
Class: |
G03G
5/06 (20060101); G03G 005/06 () |
Field of
Search: |
;96/1.5,1.6,1.7 ;252/501
;260/327,345.2 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3526502 |
September 1970 |
Murakami et al. |
3586500 |
June 1971 |
Contois et al. |
3617268 |
November 1971 |
Murakami et al. |
|
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Hightower; Judson R.
Attorney, Agent or Firm: Wenderoth, Lind & Ponack
Claims
What we claim is:
1. An electrophotographic material comprising a conductive support
layer and photoconductive insulating layer, the latter comprising a
combination of a photoconductive polymeric compound and a
sensitizing amount of a sensitizer having the following formula:
##SPC17##
wherein
B represents a radical selected from the group consisting of
##SPC18## ##SPC19##
R.sub.1 is hydrogen, phenyl or an ethenyl radical selected from the
group consisting of styryl, p-methoxystyryl, 3,4-dimethoxy-styryl,
.alpha.-phenylstyryl, .alpha.-phenyl-p-methoxystyryl,
.beta.-furyl(.alpha.')ethenyl and
.alpha.-phenyl-.beta.-furyl(.alpha.') ethenyl;
R.sub.2 is hydrogen or phenyl;
R.sub.3 is hydrogen, methyl or phenyl;
R.sub.4 is hydrogen or phenyl;
R.sub.5 is hydrogen, phenyl or an ethenyl radical selected from the
group consisting of styryl, p-methoxystyryl, 3,4-dimethoxy-styryl,
.alpha.-phenyl-p-methoxystyryl, .beta.-furyl(.alpha.')ethenyl and
.alpha.-phenyl-.beta.-furyl(.alpha.')ethenyl;
R.sub.6 is hydrogen or phenyl;
R.sub.7 is hydrogen or phenyl; .Iadd.
R.sub.8 is hydrogen or phenyl;
R.sub.9 is hydrogen or p-methoxyphenyl; .Iaddend.
the anion is an anionic function selected from the group consisting
of perchlorate, fluoroborate, chloroferrate, chlorozincate and
nitrate; and
X is oxygen or a sulfur atom;
said photoconductive polymeric compound comprising at least one
compound selected from the group consisting of
poly-N-vinylcarbazole, brominated
2. An electrophotographic material according to claim 1, wherein
said sensitizer comprises at least one compound selected from the
group consisting of
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)meth
yl]benzopyrylium perchlorate,
2-p-methoxystyryl-4-[(2'-3",4"-dimethoxystyryl-3'-phenyl-6'-methyl-4'-benz
opyranylidene)methyl]benzopyrylium perchlorate,
2-[(2'-phenyl-4'-benzopyranylidene) methyl]-3-phenyl benzopyrylium
fluoroborate,
2-[(2'-phenyl-4'-benzopyranylidene)methyl]-4-p-methoxyphenyl
benzothiopyrylium perchlorate, and
2-[(2'-phenyl-4'-benzothiopyryanylidene)methyl]-4-p-methoxyphenyl
3. An electrophotographic material according to claim 1, wherein
said combination comprises 100 weight parts of photoconductive
polymeric compound and 0.01 to 3.0 weight parts of sensitizer.
Description
This invention relates to novel light-sensitive layers and more
particularly to electrophotographic light-sensitive polymer
layers.
Various light-sensitive layers are well known in the
electrophotographic art for making copies of documents, drawings,
transparencies, etc. These layers contain organic photoconductive
compounds, such as poly-N-vinylcarbazole, brominated
poly-N-vinylcarbazoles, polyacenaphthylene, etc. These layers are
non-conductors of electricity before exposure and become electrical
conductors upon exposure.
It is necessary for the electrophotographic art that the
photoconductive material has a high photoconductivity in the long
wavelength region of the visible spectrum. Such a photoconductive
material makes it possible for the electrophotograph art to employ
inexpensive and convenient light sources such as incandescent lamps
in a reduced exposure time and to reproduce colored pictures. The
photoconductive materials mentioned above, however, have usually a
low photoconductivity and spectrum characteristics sensitive to the
short wavelength region of the exposure light and do not satisfy
entirely the above requirement.
It is known that an addition of a so-called sensitizer can improve
photoconductivity and spectrum characteristics of the above
photoconductive compounds. Conventional sensitizers are dyestuff
compounds, such as triarylmethane dyes, xanthene dyes, triazine
dyes or acridine dyes, but the conventional sensitizers are not
entirely satisfactory to improve the photoconductivity and the
spectrum characteristics of the available photoconductive
compounds.
In addition to the high photoconductivity and spectrum
characteristics sensitive to visible light, the electrophotographic
art requires a high electric resistance of photoconductive
materials in the dark. Conventional sensitizers are apt to increase
the dark conductivity whereas they promote the photoconductivity. A
high dark conductivity of photoconductive materials is not
desirable because it results in a loss of the applied electrostatic
charge in the dark.
An object of the invention is to provide electrophotographic
materials having a high photoconductivity and spectrum
characteristics sensitive to a long wavelength region of the
visible spectrum.
Another object of the invention is to provide electrophotographic
materials having a high electric resistance in the dark.
These and other objects are accomplished by adding a new sensitizer
shown hereinafter to a photoconductive polymeric compound such as
poly-N-vinylcarbazole, brominated poly-N-vinylcarbazole or
polyacenaphthylene, as a light-sensitive film-forming
composition.
The invention is further explained in the following description
with reference to the accompanying drawings wherein:
FIG. 1 represents the wedge spectrogram for an electrophotographic
material coated with an unsensitized solution of 10 weight percent
of brominated poly-N-vinylcarbazole in chlorobenzene.
FIG. 2 represents the wedge spectrogram for an electrophotographic
material coated with a solution containing 10 weight percent of
brominated poly-N-vinylcarbazole sensitized with 0.04 weight
percent of
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)-met
hyl]benzopyrylium perchlorate, the brominated poly-N-vinylcarbazole
being dissolved in a solvent of four weight parts of chlorobenzene
and one weight part of dichloroethane.
FIG. 3 represents the wedge spectrogram for an electrophotographic
material coated with a solution containing 10 weight percent of
brominated poly-N-vinylcarbazole sensitized with 0.04 weight
percent of
2-styryl-3-phenyl-4-[(2'-styryl-4'-benzopyranylidene)methyl]-6-methylbenzo
pyrylium perchlorate, the brominated poly-N-vinylcarbazole being
dissolved in a solvent of four weight parts of chlorobenzene and
one weight part of dichloroethane.
FIG. 4 represents the wedge spectrogram for an electrophotographic
material coated with a solution containing 10 weight percent of
brominated poly-N-vinylcarbazole sensitized with 0.04 weight
percent of
2-p-methoxystyryl-4-[2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranyliden
e)methyl]benzopyrylium perchlorate, the brominated
poly-N-vinylcarbazole being dissolved in a solvent of four weight
parts of chlorobenzene and one weight part of dichloroethane.
FIG. 5 represents the wedge spectrogram for an electrophotographic
material coated with a solution containing 10 weight percent of
brominated poly-N-vinylcarbazole sensitized with 0.04 weight
percent of
2-p-methoxystyryl-4-[(2'-phenyl-4'-benzothiopyranylidene)-methyl]benzopyry
lium perchlorate, the brominated poly-N-vinylcarbazole being
dissolved in a solvent of four weight parts of chlorobenzene and
one weight part of dichloroethane.
FIG. 6 represents the wedge spectrogram for an electrophotograph
material coated with a solution containing 10 weight percent of
brominated poly-N-vinyl carbazole sensitized with 0.04 weight
percent of
2-[(2'-phenyl-4'-benzopyranylidene)methyl]3-phenylbenzopyrylium
perchlorate, the brominated poly-N-vinylcarbazole being dissolved
in a solvent of four parts of chlorobenzene and one weight part of
dichloroethane.
FIG. 7 represents the wedge spectrogram for an electrophotographic
material coated with a solution containing 10 weight percent of
brominated poly-N-vinylcarbazole sensitized with 0.04 weight
percent of
2-[(4'-benzothiopyranylidene)methyl]-3-phenylbenzopyrylium
perchlorate, the brominated poly-N-vinylcarbazole being dissolved
in a solvent of four weight parts of chlorobenzene and one weight
part of dichloroethane.
FIG. 8 represents the wedge spectrogram for an electrophotographic
material coated with a solution containing 10 weight percent of
brominated poly-N-vinylcarbazole sensitized with 0.04 weight
percent of
2-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranylidene)methyl]-3-pheny
lbenzopyrylium perchlorate, the brominated poly-N-vinylcarbazole
being dissolved in a solvent of four weight parts of chlorobenzene
and one weight part of dichloroethane.
FIG. 9 represents the wedge spectrogram for an electrophotographic
material coated with a solution containing 10 weight percent of
brominated poly-N-vinylcarbazole sensitized with 0.04 weight
percent of
2-[(2'-phenyl-4'-benzothiopyranylidene)methyl]-3-phenyl-benzopyrylium
perchlorate, the brominated poly-N-vinylcarbazole being dissolved
in a solvent of four weight parts of chlorobenzene and one weight
part of dichloroethane.
The new sensitizer, according to the present invention has the
following formula: ##SPC4##
where B represents a radical selected from the group consisting of,
##SPC5## ##SPC6##
R.sub.1 is hydrogen, phenyl or an ethenyl or an ethenyl radical
selected from the group consisting of styryl,p-methoxystyryl,
3,4-dimethoxystyryl, .alpha.-phenylstyryl,
.alpha.-phenyl-p-methoxystyryl, .beta.-furyl(.alpha.')ethenyl and
.alpha.-phenyl-.beta.-furyl(.alpha.')-ethenyl;
R.sub.2 is hydrogen or phenyl;
R.sub.3 is hydrogen, methyl or phenyl;
R.sub.4 is hydrogen or phenyl;
R.sub.5 is hydrogen, phenyl or an ethenyl radical selected from the
group consisting of styryl, p-methoxystyryl, 3,4-dimethoxystyryl,
.alpha.-phenyl-p-methoxystyryl, .beta.-furyl(.alpha.')ethenyl and
.alpha.-phenyl-.beta.-furyl(.alpha.')ethenyl;
R.sub.6 is hydrogen or phenyl;
R.sub.7 is hydrogen, methyl or phenyl;
R.sub.8 is hydrogen or phenyl; .Iadd.
R.sub.9 is hydrogen or p-methoxyphenyl; .Iaddend.
the anion is anionic function selected from the group consisting of
perchlorate, fluoroborate, chloroferrate, chlorozincate and
nitrate; and
X is oxygen or sulfur atom.
The sensitizers having the formula above mentioned are prepared by
the following chemical equations A or B: ##SPC7##
In the case of Equation A,
4-[(4'-benzopyranylidene)-methyl]benzopyrylium derivative (III) is
obtained by an addition reaction of 4-methoxybenzopyrylium
o-nitrobenzene sulfonate (I) with a benzopyrylium salt (II) in an
acetic anhydride solution. The benzopyrylium salt has an active
methyl or methylene radical.
In the case of Equation B,
2-[(4'-benzopyranylidene)-methyl]benzopyrylium derivative (V) is
obtained by an addition reaction of 4-methoxybenzopyrylium
o-nitrobenzene sulfonate (I) with a benzopyrylium salt (IV) in an
acetic anhydride solution. The benzopyrylium salt has an active
methyl radical.
In both cases, methyl 2,4-dinitrobenzene sulfonate, dimethyl
sulfate or methyl iodide can be used instead of methyl
o-nitrobenzene sulfonate.
Representative examples of the benzopyranylidenemethylbenzopyrylium
salts and benzothiopyranylidene-methylbenzopyrylium salts according
to the invention are listed in Table I.
Table 1 ______________________________________ Compound Number Name
of Compound ______________________________________ 1.
2-phenyl-4-[(2'-phenyl-4'-benzopyranylidene)benzyl]-benzopyrylium
perchlorate 2.
2,3-diphenyl-4-[(2'-phenyl-4'-benzopyranylidene)-benzyl]-6-methylbe
nzopyrylium perchlorate 3.
2,3-diphenyl-4-[(2'-phenyl-4'-benzopyranylidene)-methyl]-6-methylbe
nzopyrylium perchlorate 4.
2,3-diphenyl-4-[(2'-phenyl-4'-benzopyranylidene)-methyl]-6-phenylbe
nzopyrylium perchlorate 5.
2-p-methoxystyryl-4-[(2'-phenyl-4'-benzopyranylidene)-methyl]benzop
yrylium perchlorate 6.
2-.beta.-furyl(.alpha.')ethenyl-4-[(2'-phenyl-4'-benzopyranylidene-
methyl]benzopyrylium perchlorate 7.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylide
ne)methyl]benzopyrylium perchlorate 8.
2-styryl-3-phenyl-4-[(2'-phenyl-4'-benzopyranylidene)-methyl]-6-met
hylbenzopyrylium perchlorate 9.
2-p-methoxystyryl-3-phenyl-4-[(2'-phenyl-4'-benzopyranylidene)methy
l]-6-methylbenzopyrylium perchlorate 10.
9-[(2'-phenyl-4'-benzopyranylidene)methyl]xanthylium perchlorate
11.
2-.beta.-furyl(.alpha.')ethenyl-3-phenyl-4-[(2'-phenyl-4'-benzopyra
nylidene)methyl]-6-methylbenzopyrylium perchlorate 12.
2,3-diphenyl-4-[(2'-styryl-4'-benzopyranylidene)benzyl]-6-methylben
zopyrylium perchlorate 13.
2-phenyl-4-[(2'-styryl-4'-benzopyranylidene)benzyl]benzopyrylium
perchlorate 14.
2,3-diphenyl-4-[(2'-styryl-4'-benzopyranylidene)methyl]-6-methylben
zopyrylium perchlorate 15.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-styryl-4'-benzopyranylide
ne)methyl]benzopyrylium perchlorate 16.
2-styryl-3-phenyl-4-[(2'-styryl-4'-benzopyranylidene)methyl]-6-meth
ylbenzopyrylium perchlorate 17.
9-[(2'-styryl-4'-benzopyranylidene)methyl]xanthylium perchlorate
18. 2-p-methoxystyryl-3-phenyl-4-[(2'-styryl-4'
-benzopyranylidene)meth yl]-6-methylbenzopyrylium perchlorate 19.
2,3-diphenyl-4-[(4'-benzopyranylidene)benzyl]-benzopyrylium
perchlorate 20.
2-phenyl-4-[(4'-benzopyranylidene)benzyl]benzopyrylium perchlorate
21.
2,3-diphenyl-4-[(4'-benzopyranylidene)methyl]-6-methylbenzopyrylium
perchlorate 22.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(4'-benzopyranylidene)methyl]
benzopyrylium perchlorate 23.
2-styryl-3-phenyl-4-[(4'-benzopyranylidene)methyl]-6-methylbenzopyr
ylium perchlorate 24.
2-p-methoxystyryl-3-phenyl-4-[(4'-benzopyranylidene)-methyl]-6-meth
ylbenzopyrylium perchlorate 25.
9-[(4'-benzopyranylidene)methyl]xanthylium perchlorate 26.
2-p-methoxystyryl-4-[(4'-benzopyranylidene)methyl]-benzopyrylium
perchlorate 27.
2-p-methoxystyryl-4-[(2'-p-methoxystyryl-4'-benzopyranylidene)methy
l]benzopyrylium perchlorate 28.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-p-methoxystyryl-4'-benzop
yranylidene)methyl]benzopyrylium perchlorate 29.
2-styryl-3-phenyl-4-[(2'-p-methoxystyryl-4'-benzopyranylidene)methy
l]-6-methylbenzopyrylium perchlorate 30.
2,3-diphenyl-4-[(2'-p-methoxystyryl-4'-benzopyranylidene)-methyl]-6
-methylbenzopyrylium perchlorate 31.
2,3-diphenyl-4-[(2'-p-methoxystyryl-4'-benzopyranylidene)benzyl]-6-
methylbenzopyrylium perchlorate 32.
2-phenyl-4-[(2'-p-methoxystyryl-4'-benzopyranylidene)-benzyl]benzop
yrylium perchlorate 33.
9-[(2'-p-methoxystyryl-4'-benzopyranylidene)methyl]-xanthylium
perchlorate 34.
2-p-methoxystyryl-4-[(4'-benzothiopyranylidene)methyl]-benzopyryliu
m perchlorate 35.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(4'-benzothiopyranylidene)-me
thyl]benzopyrylium perchlorate 36.
2-styryl-3-phenyl-4-[(4'-benzothiopyranylidene)methyl]-6-methylbenz
opyrylium perchlorate 37.
2,3-diphenyl-4-[(4'-benzothiopyranylidene)methyl]-6-methylbenzopyry
lium perchlorate 38. 2,3-diphenyl-4-[
(4'-benzothiopyranylidene)benzyl]-6-methylbenzopy rylium
perchlorate 39.
2-phenyl-4-[(4'-benzothiopyranylidene)benzyl]benzopyrylium
perchlorate 40. 9-[(4'-benzothiopyranylidene)methyl]xanthylium
perchlorate. 41.
2-p-methoxystyryl-3-phenyl-4-[(4'-benzothiopyranylidene)-methyl]-6-
methylbenzopyrylium perchlorate 42.
2-p-methoxystyryl-4-[(2'-3",4"-dimethoxystyryl-4'-benzopyranylidene
)methyl]benzopyrylium perchlorate 43.
2-styryl-3-phenyl-4-[(2'-3",4"-dimethoxystyryl-4'-benzopyranylidene
)methyl]-6-methylbenzopyrylium perchlorate 44.
9-[(2'-3",4"-dimethoxystyryl-4'-benzopyranylidene)-methyl]xanthyliu
m perchlorate 45.
2-phenyl-4-[(2'-.beta.-furyl(.alpha.')ethenyl-4'-benzopyranylidene)
-benzyl]benzopyrylium perchlorate 46.
2,3-diphenyl-4-[(2'-.beta.-furyl(.alpha.')ethenyl-4'-benzopyranylid
ene)benzyl]-6-methylbenzopyrylium perchlorate 47.
2,3-diphenyl-4-[(2'-.beta.-furyl(.alpha.')ethenyl-4'-benzopyranylid
ene)methyl]-6-methylbenzopyrylium perchlorate 48.
2-p-methoxystyryl-4-[(2'-.beta.-furyl(.alpha.')ethenyl-4'-benzopyra
nylidene)methyl]benzopyrylium perchlorate 49.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-.beta.-furyl(.alpha.')eth
enyl-4'-benzopyranylidene)methyl]benzopyrylium perchlorate 50.
9-[(2'-.beta.-furyl(.alpha.')ethenyl-4'-benzopyranylidene)methyl]-x
anthylium perchlorate 51.
2-phenyl-4-[(2'-.alpha.-phenylstyryl-4'-benzopyranylidene)-benzyl]b
enzopyrylium perchlorate 52.
2-p-methoxystyryl-4-[(2'-.alpha.-phenylstyryl-4'-benzopyranylidene)
methyl]benzopyrylium perchlorate 53.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-.alpha.-phenylstyryl-4'-b
enzopyranylidene)methyl]benzopyrylium perchlorate 54.
2-phenyl-4-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranylidene
)benzyl]benzopyrylium perchlorate 55.
2,3-diphenyl-4-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranyli
dene)benzyl] -6-methylbenzopyrylium perchlorate 56.
2,3-diphenyl-4-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranyli
dene)methyl]-6-methylbenzopyrylium perchlorate 57.
2-p-methoxystyryl-4-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyr
anylidene)methyl]benzopyrylium perchlorate 58.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-.alpha.-phenyl-p-methoxys
tyryl-4'-benzopyranylidene)methyl] benzopyrylium perchlorate 59.
9-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranylidene)-methyl]
xanthylium perchlorate 60.
2-p-methoxystyryl-4-[(2'-.alpha.-phenyl-.beta.-furyl(.alpha.')ethen
yl-4'-benzopyranylidene)methyl]benzopyrylium perchlorate 61.
9-[(2'-.alpha.-phenyl-.beta.-furyl(.alpha.')ethenyl-4'-benzopyranyl
idene)methyl]xanthylium perchlorate 62.
2-phenyl-4-[(2'-p-methoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranyl
idene)benzyl]benzopyrylium perchlorate 63.
2,3-diphenyl-4-[(2'-p-methoxystyryl-3'-phenyl-6'-methyl-4'-benzopyr
anylidene)benzyl]-6-methylbenzopyrylium perchlorate 64.
2,3-diphenyl-4-[(2'-p-methoxystyryl-3'-phenyl-6'-methyl-4'-benzopyr
anylidene)methyl]-6-methylbenzopyrylium perchlorate 65.
2-p-methoxystyryl-4-[(2'-p-methoxystyryl-3'-phenyl-6'-methyl-4'-ben
zopyranylidene)methyl]benzopyrylium perchlorate 66.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-p-methoxystyryl-3'-phenyl
-6'-methyl-4'-benzopyranylidene)methyl]benzopyrylium perchlorate
67.
9-[(2'-p-methoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranylidene)met
hyl]xanthylium perchlorate 68.
2-phenyl-4-[(2'-3",4"-dimethoxystyryl-3'-phenyl-6'-methyl-4'-benzop
yranylidene)benzyl]benzopyrylium perchlorate 69.
2,3-diphenyl-4-[(2'-3",4"-dimethoxystyryl-3'-phenyl-6'-methyl-4'-be
nzopyranylidene)benzyl]-6-methylbenzopyrylium perchlorate 70.
2,3-diphenyl-4-[(2'-3",4"-dimethoxystyryl-3'-phenyl-6'-methyl-4'-be
nzopyranylidene)methyl] -6-methylbenzopyrylium perchlorate 71.
2-p-methoxystyryl-4-[(2'-3",4"-dimethoxystyryl-3'-phenyl-6'-methyl-
4'-benzopyranylidene)methyl]benzopyrylium perchlorate 72.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-3",4"-dimethoxystyryl-3'-
phenyl-6'-methyl-4'-benzopyranylidene)methyl]-benzopyrylium
perchlorate 73.
9-[(2'-3",4"-dimethoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranylide
ne)methyl]xanthylium perchlorate 74.
2-phenyl-4-[(2'-.beta.-furyl(.alpha.')ethenyl-3'-phenyl-6'-methyl-4
'-benzopyranylidene)benzyl]benzopyrylium perchlorate 75.
2,3-diphenyl-4-[(2'-.beta.-furyl (.alpha.')ethenyl-3'-phenyl-6'-met
hyl-4'-benzopyranylidene)benzyl]-6-methylbenzopyrylium perchlorate
76.
2,3-diphenyl-4-[(2'-.beta.-furyl(.alpha.')ethenyl-3'-phenyl-6'-meth
yl-4'-benzopyranylidene)methyl]-6-methylbenzopyrylium perchlorate
77.
2-p-methoxystyryl-4-[(2'-.beta.-furyl(.alpha.')ethenyl-3'-phenyl-6'
-methyl-4'-benzopyranylidene)methyl]benzopyrylium perchlorate 78.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-.beta.-furyl(.alpha.')eth
enyl-3'-phenyl-6'-methyl-4'-benzopyranylidene)methyl]-benzopyrylium
perchlorate 79.
9-[(2'-.beta.-furyl(.alpha.')ethenyl-3'-phenyl-6'-methyl-4'-benzopy
ranylidene)methyl]xanthylium perchlorate 80.
2-phenyl-4-[(2'-phenyl-4'-benzothiopyranylidene)benzyl]-benzopyryli
um perchlorate 81.
2,3-diphenyl-4-[(2'-phenyl-4'-benzothiopyranylidene)-benzyl]-6-meth
ylbenzopyrylium perchlorate 82.
2,3-diphenyl-4-[(2'-phenyl-4'-benzothiopyranylidene)-methyl]-6-meth
ylbenzopyrylium perchlorate 83.
2-p-methoxystyryl-4-[(2'-phenyl-4'-benzothiopyranylidene)methyl]ben
zopyrylium perchlorate 84.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzothiopyrany
lidene)methyl]benzopyrylium perchlorate 85.
2-p-methoxystyryl-3-phenyl-4-[(2'-phenyl-4'-benzothiopyranylidene)m
ethyl] -6-methylbenzopyrylium perchlorate 86.
2-styryl-3-phenyl-4-[(2'-phenyl-4'-benzothiopyranylidene)methyl]-6-
methylbenzopyrylium perchlorate 87.
9-[(2'-phenyl-4'-benzothiopyranylidene)methyl]xanthylium
perchlorate 88.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylide
ne)methyl]benzopyrylium fluoborate 89.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylide
ne)methyl]benzopyrylium chloroferrate 90.
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylide
ne)methyl]benzopyrylium chlorozincate 91.
2-[(2'-phenyl-4'-benzopyranylidene)methyl]-benzopyrylium
perchlorate 92.
2-[(2'-phenyl-4'-benzopyranylidene)methyl]-3-phenylbenzopyrylium
perchlorate 93.
2-[(2'-phenyl-4'-benzopyranylidene)methyl]-3-phenylbenzopyrylium
fluoborate 94.
2-[(2'-phenyl-4'-benzopyranylidene)methyl]-3-phenylbenzopyrylium
chloroferrate 95.
2-[(2'-phenyl-4'-benzopyranylidene)methyl]-3-phenylbenzopyrylium
nitrate 96. 2-[(2'-styryl-4'-benzopyranylidene)methyl]benzopyrylium
perchlorate 97.
2-[(2'-styryl-4'-benzopyranylidene)methyl]-3-phenylbenzopyrylium
perchlorate 98. 2-[(4'-benzopyranylidene)methyl]benzopyrylium
perchlorate 99.
2-[(4'-benzopyranylidene)methyl]-3-phenylbenzopyrylium perchlorate
100.
2-[(2'-p-methoxystyryl-4'-benzopyranylidene)methyl]-benzopyrylium
perchlorate 101.
2-[(2'-p-methoxystyryl-4'-benzopyranylidene)methyl]-3-phenylbenzopy
rylium perchlorate 102.
2-[(4'-benzothiopyranylidene)methyl]benzopyrylium perchlorate 103.
2-[(4'-benzothiopyranylidene)methyl]-3-phenylbenzopyrylium
perchlorate 104.
2-[(2'-3",4"-dimethoxystyryl-4'-benzopyranylidene)-methyl]benzopyry
lium perchlorate 105.
2-[(2'-3",4"-dimethoxystyryl-4'-benzopyranylidene)-methyl]-3-phenyl
benzopyrylium perchlorate 106.
2-[(2'-.beta.-furyl(.alpha.')ethenyl-4'-benzopyranylidene)methyl]-b
enzopyrylium perchlorate 107.
2-[(2'-.beta.-furyl(.alpha.')ethenyl-4'-benzopyranylidene)methyl]-3
-phenylbenzopyrylium perchlorate 108.
2-[(2'-.alpha.-phenylstyryl-4'-benzopyranylidene)methyl]-benzopyryl
ium perchlorate 109.
2-[(2'-.alpha.-phenylstyryl-4'-benzopyranylidene)methyl]-3-phenylbe
nzopyrylium perchlorate 110.
2-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranylidene)-methyl]
benzopyrylium perchlorate 111.
2-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranylidene)-methyl]
-3-phenylbenzopyrylium perchlorate 112.
2-[(2'-.alpha.-phenyl-.beta.-furyl(.alpha.')ethenyl-4'-benzopyranyl
idene)methyl]-3-phenylbenzopyrylium perchlorate 113.
2-[(2'-p-methoxystyryl-3',6'-diphenyl-4'-benzopyranylidene)methyl]-
3-phenylbenzopyrylium perchlorate 114.
2-[(2'-3",4"-dimethoxystyryl-3',6'-diphenyl-4'-benzopyranylidene)me
thyl]-3-phenylbenzopyrylium perchlorate 115.
2-[(2'-p-methoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranylidene)met
hyl]benzopyrylium perchlorate 116.
2-[(2'-p-methoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranylidene)met
hyl]-3-phenylbenzopyrylium perchlorate 117.
2-[(2'-3",4",-dimethoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranylid
ene)methyl]benzopyrylium perchlorate 118.
2-[(2'-3",4"-dimethoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranylide
ne)methyl]-3-phenylbenzopyrylium perchlorate 119.
2-[(2'-.beta.-furyl(.alpha.')ethenyl-3'-phenyl-6'-methyl-4'-benzopy
ranylidene)methyl]benzopyrylium perchlorate 120.
2-[(2'-.beta.-furyl(.alpha.')ethenyl-3'-phenyl-6'-methyl-4'-benzopy
ranylidene)methyl]-3-phenylbenzopyrylium perchlorate 121.
2-[(2'-phenyl-4'-benzothiopyranylidene)methyl]benzopyrylium
perchlorate 122.
2-[(2'-phenyl-4'-benzothiopyranylidene)methyl]-3-phenylbenzopyryliu
m perchlorate 123.
2-[(2'-phenyl-4'-benzopyranylidene)methyl]-4-p-methoxyphenylbenzoth
iopyrylium perchlorate 124.
2-[(2'-phenyl-4'-benzopyranylidene)methyl]-3-phenyl-4-p-methoxyphen
ylbenzopyrylium perchlorate 125.
2-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranylidene)-methyl]
-4-p-methoxyphenylbenzothiopyrylium perchlorate 126.
2-[(2'-.alpha.-phenyl-p-methoxystyryl-4'-benzopyranylidene)-methyl]
-3-phenyl-4-p-methoxyphenylbenzothiopyrylium perchlorate 127.
2-[(2'-phenyl-4'-benzothiopyranylidene)methyl]-4-p-methoxyphenylben
zothiopyrylium perchlorate 128.
2-[(2'-phenyl-4'-benzothiopyranylidene)methyl]-3-phenyl-4-p-methoxy
phenylbenzothiopyrylium perchlorate
______________________________________ Table 2 lists additional
information on the absorption maximum in dichloroethane and melting
point of the novel compounds according to the invention.
Table 2 ______________________________________ Compound Absorption
Maximum Number Melting Point in dichloroethane (m.mu.)
______________________________________ 1 135.about.139 415 and 710
2 130.about.132 430 and 720 3 182.about.187 410 and 630 4
164.about.170 635 5 163.about.172 490 and 575 6 >300 575 and 660
7 162.about.169 500 and 610 8 180.about.187 490 and 670 9
157.about.160 550 and 670 10 103.about.105 610 11 120.about.126 595
12 176.about.180 430 and 700 13 122.about.126 420 and 730 14
163.about.170 420 and 650 15 160.about.164 500 and 600 16
166.about.169 495 and 710 17 135.about.140 580 18 159.about.162 555
19 179.about.181 420 and 730 20 140.about.142 415 and 730 21
165.about.172 410 and 700 22 174.about.178 500 and 600 23
176.about.179 485 24 170.about.175 505 25 >300 630 26 >300
560 27 191.about.197 560 28 201.about.203 500 and 590 29
200.about.204 660 and 710 30 185.about.189 410 and 650 31
178.about.183 430 and 690 32 181.about.188 420 and 700 33
117.about.123 550 and 650 34 185.about.189 590 35 159.about.164 495
and 600 36 185.about.188 610, 650 and 700 37 160.about.165 415 and
650 38 204.about.206 425 and 700 39 166.about.169 415 and 730 40
>300 660 41 173.about.180 555 42 175.about.181 540 and 600 43
167.about.173 660 and 710 44 161.about.164 580 and 720 45
145.about.150 415 and 720 46 188.about.190 425 and 720 47
168.about.175 670 48 171.about.176 490 and 580 49 179.about.186 600
and 720 50 171.about.175 610 and 660 51 151.about.155 480 and 740
52 171.about.176 495 and 580 53 173.about.177 590 and 700 54
140.about.147 550 and 750 55 203.about.207 420 and 680 56
138.about. 142 555 and 680 57 170.about.175 570 58 154.about.157
585 and 690 59 168.about.174 570 60 206.about.209 600 61 >300
650 62 139.about.146 550 63 202.about.204 425 and 700 64
173.about.177 530 and 690 65 190.about.194 590 66 190.about.193 500
and 600 67 192.about.195 620 68 112.about.118 570 and 760 69
190.about.192 495 70 154.about.159 650 and 700 71 177.about.182 500
and 710 72 176.about.181 590 73 195.about.199 495 and 640 74
189.about.195 550 75 184.about.187 415 and 720 76 192.about.196 640
and 700 77 >300 550 78 219.about.222 550 79 226.about.230 630 80
127.about.134 410 and 745 81 190.about.192 425 and 730 82
156.about.159 665 83 164.about.169 600 and 680 84 175.about. 178
600 and 720 85 170.about.177 550 and 700 86 157.about.166 650 and
695 87 169.about.172 635 88 137.about.140 500 and 610 89
167.about.172 500 and 610 90 160.about.163 500 and 610 91 >300
575 92 128.about.134 575 and 675 93 133.about.136 575 and 675 94
152.about.158 575 and 675 95 133.about.138 575 96 190.about.195 575
97 156.about.158 620 and 690 98 225.about.229 565 99 183.about.187
525 and 560 100 208.about.212 570 101 170.about.176 630 and 690 102
225.about.228 610 103 163.about.168 610 and 690 104 178.about.184
510 105 172.about.175 580 and 690 106 167.about.171 565 and 620 107
190.about.194 560 and 635 108 211.about.214 570 and 610 109
175.about.179 570 and 610 110 198.about.201 570 and 610 111
158.about.163 580 and 630 112 >300 600 and 645 113 185.about.188
570 and 620 114 199.about.204 600 115 211.about.215 565 and 600 116
177.about.181 570 and 610 117 205.about.207 570 118 190.about.194
590 119 237.about.241 560 120 >300 590 121 207.about.210 565 and
605 122 155.about.158 615 and 675 123 143.about.145 615 124
126.about.131 619 125 144.about.148 559 and 657 126 140.about.142
589 and 663 127 149.about.153 656
128 141.about.145 660 ______________________________________
The following description will explain a practical method for
making benzopyranylidene-methylbenzopyrylium salts or
benzothiopyranylidene-methylbenzopyrylium salts with reference to
exemplary compounds. The details of the preparation of other
compounds will be apparent to the skilled in the art from the
preceding disclosure and the following illustrative examples of
preparation methods of various compounds according to the
invention:
(a)
2-phenyl-4-[(2'-phenyl-4'-benzopyranylidene)-benzyl]benzopyrylium
perchlorate (compund number 1) ##SPC8##
5.5 Grams of 2-phenyl-4-methoxybenzopyrylium o-nitrobenzene
sulfonate, which is obtained from flavone and methyl
o-nitrobenzenesulfonate, and 5 grams of
2-phenyl-4-benzylbenzopyrylium perchlorate are dissolved in 150
milliliters of acetic anhydride to a solution. The solution is then
refluxed for 15 minutes and poured into 900 milliliters of 10
weight percent perchloric acid. The solution is filtered to obtain
a precipitate. The precipitate is dried and dissolved again in
dichloroethan to a solution. For purification the solution is
poured into ether. Precipitated crystals are filtered off, washed
with ether and dried to obtain 4 grams (theoretical yield 53%) of
green crystals having a melting point of 135.degree. to 139.degree.
C.
(b)
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)meth
yl]benzopyrylium perchlorate (compound number 7) ##SPC9##
5.5 grams of
2-(.alpha.-phenyl-p-methoxystyryl)-4-methylbenzopyrylium
perchlorate and 5.5 grams of 2-phenyl-4-methoxybenzopyrylium
o-nitrobenzene sulfonate are dissolved in 150 milliliters of acetic
anhydride to a solution. The solution is then refluxed for 15
minutes and poured into 900 milliliters of 10 weight percent
perchloric acid. The solution is filtered to obtain a precipitate.
The precipitate is reprecipitated with dichloroethane ether.
Precipitated crystals are filtered off, washed with ether and dried
to obtain 5.5 grams (theoretical yield 69%) of blue crystals having
a melting point of 162.degree. to 169.degree.C. In the procedure
above mentioned the solution ios poured into an ether solution of
BF.sub.3.O(C.sub.2 H.sub.5).sub.2 instead of 10 weight percent
perchloric acid. In this case
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)meth
yl]benzopyrylium fluoroborate (compound number 88) is obtained. In
the procedure when the solution is poured into a 10 weight percent
zinc chloride aqueous solution,
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)-met
hyl]benzopyrylium chlorozincate (compound number 90) is
obtained.
(c)
2-p-methoxystyryl-3-phenyl-4-[(2'-styryl-4'-benzopyranylidene)methyl]-6-me
thylbenzopyrylium perchlorate (compound number 18) ##SPC10##
2-styryl-4-methoxybenzopyrylium o-nitrobenzenesulfon (melting
point, 155.degree. to 157.degree. C) is obtained by a reaction of
2-styrylchromone and methyl o-nitrobenzenesulfonate in dry benzene
at 50.degree. C for 24 hours. According to the same reaction as
shown in procedure (a), 2-styryl-4-methoxybenzopyrylium
o-nitrobenzenesulfonate reacts with
2-p-methoxystyryl-3-phenyl-4,6-dimethylbenzopyrylium perchlorate to
obtain
2-p-methoxystyryl-3-phenyl-4-[(2'-styryl-4'-benzopyranylidene)methyl]-6-me
thylbenzopyrylium perchlorate crystals which have a color of
reddish violet in dichloroethane and have a melting point of
159.degree. to 162.degree. C. The product is obtained in 73%
yield.
(d)
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(4'-benzopyranylidene)-methyl]benzop
yrylium perchlorate (compound number 22) ##SPC11##
4-methoxybenzopyrylium o-nitrobenzenesulfonate reacts with
2-(.alpha.-phenyl-p-methoxystyryl)-4-methyl]benzopyrylium
perchlorate to
2-(.alpha.-phenyl-p-methoxystyryl)-4-[(4'-benzopyranylidene)methyl]-benzop
yrylium perchlorate in the same procedure as the procedure (a). The
crystals have a color of violet in dichloroethane and a melting
point of 174.degree. to 178.degree.C. The product is obtained in
95% yield.
(e)
2-p-methoxystyryl-4-[(2'-3",4"-dimethoxystyryl-4'-benzopyranylidene)methyl
]benzopyrylium perchlorate (compound number 42) ##SPC12##
2-(3',4'-Dimethoxystyryl)-4-methoxybenzopyrylium
o-nitrobenzenesulfonate (melting point 211.degree. to 213.degree.C)
is obtained from a reaction of 2-(3',4'-dimethoxystyryl)chromone
and methyl o-nitrobenzene sulfonate. 6.5 Grams of
2-(3',4'-dimethoxystyryl)-4-methoxybenzopyrylium
o-nitrobenzenesulfonate and 4,5 grams of
2-p-methoxystyryl-4-methylbenzopyrylium perchlorate are dissolved
in 150 milliliters of acetic anhydride to a solution. The solution
is heated at 100.degree.C for 100 minutes. After cooling the
solution is poured into 900 milliliters of 10 weight percent
perchloric acid. Precipitates are filtered off and dried. For
purification, reprecipitation is made using dichlorethane and
ether. 3.2 Grams of product is obtained in 41% yield. The product
has a color of drak violet in dichloroethane and a melting point of
175.degree. to 181.degree.C.
(f)
2-(.alpha.-phenyl-p-methoxystyryl)-4-(2'-p-methoxystyryl-3'-phenyl-6'-meth
yl-4'-benzopyranylidene)methyl]-benzopyrylium perchlorate (compound
number 66) ##SPC13##
2-p-Methoxystyryl-3-phenyl-4-methoxy-6-methylbenzopyrylium
o-nitrobenzenesulfonate (melting point 141.degree. to 144.degree.C)
is obtained from 2-p-methoxystyryl-3-phenyl-6-methylchromone and
methyl o-nitrobenzenesulfonate.
2-p-methoxystyryl-3-phenyl-4-methoxy-6-methylbenzopyrylium
o-nitrobenzenesulfonate reacts with
2-(.alpha.-phenyl-p-methoxystyryl)-4-methylbenzopyrylium
perchlorate in the same procedure as the procedure (e). The product
has a color of violet in dichloroethane and a melting point of
190.degree. to 193.degree. C.
(g)
2-p-methoxystyryl-3-phenyl-4-[(2'-phenyl-4'-benzothiopyranylidene)methyl]-
6-methyl]benzopyrylium perchlorate (compound number 85)
##SPC14##
2-phenyl-4-methoxybenzothiopyrylium o-nitrobenzenesulfonate is
obtained from thioflavone and methyl o-nitrobenzenesulfonate. As
the same procedure as procedure (e), the product is obtained in 62%
yield. The product has a color of reddish violet in dichloroethane
and a melting point of 170.degree. to 177.degree. C.
(h)
2-[(2'-phenyl-4'-benzopyranylidene)methyl]-3-phenylbenzopyrylium
perchlorate (compound number 92) ##SPC15##
5.5 grams of 2-phenyl-4-methoxybenzopyrylium
o-nitrobenzenesulfonate, which is obtained from flavone and methyl
o-nitrobenzenesulfonate, and 4 grams of
2-methyl-3-phenylbenzopyrylium perchlorate are dissolved in 150
milliliters of acetic anhydride to a solution. The solution is
heated at 100.degree. C for 15 minutes. After cooling the solution
is poured into 900 milliliters of 10 weight percent perchloric
acid. Precipitated product is filtered off and dried. For
purification, reprecipitation is made using dichloroethane and
ether. The product has a color of blue in dichloroethane and a
melting point of 128.degree. to 134.degree. C. The product yields 3
grams (theoretical yield 46%). Compound number 93 (fluoborate),
compound number 94 (chloroferrate) or compound number 95 (nitrate)
is obtained using either solution of borontrifluoride etherate,
aqueous solution of ferric chloride or diluted nitric acid
respectively instead of 10 weight percent perchloric acid.
(i)
2[(2'-4-phenyl-p-methoxystyryl-4'-benzopyranylidene)methyl]-3-phenylbenzop
yrylium perchlorate (compound number 11) ##SPC16##
2-(.alpha.-Phenyl-p-methoxystyryl)-4-methoxybenzopyrylium
o-nitrobenzenesulfonate, which is obtained from
2-(.alpha.-phenyl-p-methoxystyryl)chromone and methyl
o-nitrobenzenesulfonate, reacts with 2-methyl-3-phenylbenzopyrylium
perchlorate in the same procedure as procedure (h). The reaction
product yields in 43%. The product has a color of violet in
dichloroethane and a melting point of 158.degree. to
163.degree.C.
It has been discovered according to the invention the compounds
listed in Table 1 are sensitizing agents which can improve the
photoconductivity and the spectrum characteristics of
photoconductive polymeric compounds such as poly-N-vinylcarbazole,
brominated poly-N-vinylcarbazoles, polyacenaphthylene, etc. These
polymers, except brominated poly-N-vinylcarbazoles, are prepared in
a per se well known method. The brominated poly-N-vinylcarbazole
can be prepared by the following method: To the solution of 20
grams of poly-N-vinylcarbazole in 450 milliliters of chlorobenzene,
there are added 18.44 grams of N-bromosuccinimide and 0.173 grams
of benzoyl peroxide. The mixture is heated at 80.degree.C for 2
hours while being stirred thoroughly and is poured into methanol to
obtain a white polymer. The polymer is dissolved in chlorobenzene
and again poured into methanol for purification. The pure polymer
thus obtained as a precipitate exhibits upon elementary analysis a
halogen content of 29.87 weight percent which approximates the
value calculated, i.e. 29.44 weight percent of the
monobromosubstituted product from poly-N-vinylcarbazole. This
indicates that the polymer obtained is a monobromosubstituted
product. The degree of bromination varies from 50 mole percent to
200 mole percent according to reaction conditions.
The novel sensitizer comprising at least one compound from the
group listed in Table 1 is dissolved in a suitable solvent, such as
dichloroethane, methylene chloride, chloroform, or a combination
thereof, and is added to the solution of the photoconductive
polymer described above. The preferable amount of the sensitizer
added is from 0.01 to 3.0 weight parts in connection with 100
weight parts of the photoconductive polymer. Advantageously, the
amount thereof is from 0.1 to 2.0 weight parts in connection with
100 weight parts of the photoconductive polymer.
For the preparation of the photoconductive insulating layer, a said
solution of the photoconductive polymer and the sensitizer in a
suitable solvent is applied to the electroconductive support in per
se usual manner, for example, by spraying, by means of bladed
coating, by means of whirler coating, etc., and then dried so as to
produce a homogeneous photoconductive insulating layer on the
electroconductive support. Operable solvents are benzene, toluene,
chlorobenzene, dioxane, methylene chloride, dichloroethane and
combinations thereof. Said solution may be incorporated with
suitable plasticizers and/or organic colloids for improving the
flexibility and strength of the photoconductive polymer. Operable
plasticizers are as follows: chlorinated diphenyl, dimethyl
phthalate, diethyl phthalate and octyl phthalate. Operable organic
colloids are as follows: natural and synthetic resins, e.g. phenol
resin, phenol resin modified with resin, polyvinyl acetal,
polyvinyl butyral, polyvinyl cinnamate, polycarbonate resin.
Operable materials for electroconductive supports may be made of
any materials which satisfy the requirement of the
electrophotographic art, e.g. metal plate or glass plate having
NESA coating, plate or foil made of electrically conductive resin
or coated with evaporated thin metal layer. If paper is to be used
as a support for the photoconductive layer, pretreatment of the
paper against penetration of the coating solution in advisable. The
transparent support can produce a transparent electrophotographic
plate, foil or film. After an electrostatic charge has been
applied, i.e. after the layer has been charged positively or
negatively by means of a corona discharge, the layer becomes light
sensitive.
The reproduction of images by the electrophotographic method is
carried out as follows: when the photoconductive layer has been
charged by means of a corona discharge apparatus, the support with
the sensitized layer is exposed to light under a master and is then
dusted over in a per se known manner with a resin powder colored
with carbon black. The image that now becomes visible can easily be
wiped off. It can also be fixed by heating at about 120.degree.C.
From positive masters, positive images characterized by good
contrast the producted.
This invention is still further illustrated with reference to the
following illustrative examples.
EXAMPLE 1
1 Gram of polyacenaphthylene and 0.6 gram of, as a plasticiser,
chlorinated diphenyl (commercially available as "Kanechlor"), are
dissolved in 8 milliliters of chlorobenzene. To the solution are
added 0.5 milliliters of dichloroethane containing 0.006 gram of a
sensitizer corresponding to compound number listed in Table 1. The
solution is applied to an aluminum plate by means of whirler
coating and is dried to form a layer of 7.mu. in thickness. After
said aluminum plate provided with the layer is charged negatively
by means of corona discharge with a charging device maintained at
approximately 6000 volts in the dark, it is placed under a positive
master and is exposed to a 100W tungsten lamp at an illumination of
50 luxes, and the said plate is powdered over with a developer in a
per se known manner. This developer consists of toner and carrier.
The toner consists of low melting point polystyrene, colophony and
carbon black. The toner is mixed with a carrier substance such that
the toner becomes triboelectrically charged with a charge opposite
to that produced on the plate. A positive image is produced and is
fixed by slight heating. In Table 2, there are shown the optimum
amounts of exposure in lux-second units.
Table 2 ______________________________________ Compound Number
Optimum Exposure (lux.sec) ______________________________________
none 200000 5 320 7 300 9 75 15 180 16 110 18 65 33 135 35 480 41
105 42 320 51 380 52 140 53 290 54 140 58 130 60 175 65 140 71 180
92 70 97 150 103 100 105 120 109 130 110 180 111 70 112 170 113 120
116 115 ______________________________________
EXAMPLE 2
1 Gram of poly-N-vinylcarbazole, chlorinated diphenyl (commercially
available as "Kanechlor") and 0.006 gram of a sensitizer,
coresponding to compound number listed in Table 1, in 10
milliliters of dichloroethane to a solution. The solution is
applied to an aluminum plate by means of blade coating and is dried
to form a layer of 10.mu. in thickness. An electrophotographic
image in the same way as that described in Example 1. In Table 3,
there are shown the optimum amounts of exposure in lux-second units
to produced exactly the original images.
Table 3 ______________________________________ Compound Number
Optimum Exposure (lux.sec) ______________________________________
none 20000 1 50 2 220 3 60 4 70 5 22 6 44 7 26 8 62 9 44 10 48 11
160 12 220 13 90 14 75 15 28 16 36 17 115 18 22 23 180 26 110 27 44
28 36 29 40 30 60 32 120 33 36 34 50 35 30 36 46 37 90 41 52 42 44
43 48 45 75 47 58 48 34 49 35 50 70 51 30 53 26 54 28 56 28 57 20
58 24 59 36 60 44 61 44 62 100 64 54 65 44 66 22 67 74 70 56 71 20
72 22 76 60 78 38 80 46 82 50 83 24 84 19 85 17 86 54 87 42 88 25
89 28 90 30 91 140 92 18 93 20 34 23 95 40 96 66 29 24 98 230 99
460 100 50 101 36 102 115 103 36 104 68 105 19 106 120 107 58 108
76 109 46 110 36 111 20 112 42 113 48 114 54 115 54 116 52 117 64
118 50 119 135 120 90 121 30 122 28
______________________________________
It is clear from Table 3 that the novel sensitizers improve the
photoconductivity of poly-N-vinylcarbazole.
EXAMPLE 3
1 Gram of brominated poly-N-vinylcarbazole (monobromo-substituted
product), 0.5 gram of polycarbonate resin (commercially available
as "Panlite-C"), 0.3 gram of chlorinated diphenyl (commercially
available as "Kanechlor") and 0.002 gram of sensitizer listed in
Table 1 are dissolved in a mixed-solvent of 8 milliliters of
chlorobenzene and 2 milliliters of dichloroethane. This solution is
applied to an aluminum plate by means of a blade coating and dried
to form a layer of 14.mu. in thickness. On this support,
electrophotographic images are produced in the same way as that
described in Example 1. Table 4 shows the optimum amounts of
exposure in lux-second units to reproduce exactly the original
images.
Table 4 ______________________________________ Compound Number
Optimum Exposure (lux.sec) ______________________________________
none 80000 1 75 2 280 3 67 4 44 5 20 6 26 7 18 8 30 9 22 10 40 11
120 12 400 13 110 14 75 15 25 16 28 17 135 18 23 19 410 20 340 21
180 22 40 23 130 24 60 25 300 26 100 27 52 28 52 29 48 30 110 31
320 32 270 33 27 34 30 35 26 37 52 38 440 39 110 40 125 41 22 42 28
43 32 44 75 45 105 46 170 47 42 48 32 49 35 50 50 51 48 52 20 53 19
54 42 55 230 56 26 57 22 58 24 59 23 60 26 61 36 62 130 63 190 64
44 65 26 66 20 67 46 68 75 69 115 70 42 71 18 72 20 73 48 74 110 75
115 76 70 77 44 78 35 79 75 80 50 81 145 82 35 83 20 84 19 85 17 86
34 87 34 88 20 89 20 90 25 91 100 92 15 93 17 94 16 95 40 96 52 97
26 98 180 99 140 100 46 101 36 102 58 103 20 104 34 105 21 106 80
107 44 108 40 109 23 110 26 111 17 112 26 113 28 114 40 115 44 116
28 117 44 118 36 119 105 120 52 121 26 122 21 123 15 124 25 125 17
126 14 127 11 128 13 ______________________________________
It is clear from Table 4 and FIGS. 1 to 9 that the novel
sensitizers improve the photoconductivity and the spectrum
characteristics of brominated poly-N-vinylcarbazole.
The invention has been described in detail with particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention as described hereinabove and
as defined in the appended claims.
* * * * *