USRE28698E - Electrophotographic material containing sensitizers - Google Patents
Electrophotographic material containing sensitizers Download PDFInfo
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- USRE28698E USRE28698E US05/495,520 US49552074A USRE28698E US RE28698 E USRE28698 E US RE28698E US 49552074 A US49552074 A US 49552074A US RE28698 E USRE28698 E US RE28698E
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- Prior art keywords
- phenyl
- methyl
- perchlorate
- benzopyranylidene
- methoxystyryl
- Prior art date
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0664—Dyes
- G03G5/0666—Dyes containing a methine or polymethine group
- G03G5/0672—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups
- G03G5/0674—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups containing hetero rings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0664—Dyes
- G03G5/0666—Dyes containing a methine or polymethine group
- G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group
- G03G5/067—Dyes containing a methine or polymethine group containing only one methine or polymethine group containing hetero rings
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.
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-(α-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)-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. 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-methylbenzopyrylium 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'-α-phenyl-p-methoxystyryl-4'-benzopyranylidene)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]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. 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'-α-phenyl-p-methoxystyryl-4'-benzopyranylidene)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. 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##
R1 is hydrogen, phenyl or an ethenyl or an ethenyl radical selected from the group consisting of styryl,p-methoxystyryl, 3,4-dimethoxystyryl, α-phenylstyryl, α-phenyl-p-methoxystyryl, β-furyl(α')ethenyl and α-phenyl-β-furyl(α')-ethenyl;
R2 is hydrogen or phenyl;
R3 is hydrogen, methyl or phenyl;
R4 is hydrogen or phenyl;
R5 is hydrogen, phenyl or an ethenyl radical selected from the group consisting of styryl, p-methoxystyryl, 3,4-dimethoxystyryl, α-phenyl-p-methoxystyryl, β-furyl(α')ethenyl and α-phenyl-β-furyl(α')ethenyl;
R6 is hydrogen or phenyl;
R7 is hydrogen, methyl or phenyl;
R8 is hydrogen or phenyl; .Iadd.
R9 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-β-furyl(α')ethenyl-4-[(2'-phenyl-4'-benzopyranylidene-
methyl]benzopyrylium perchlorate
7. 2-(α-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-β-furyl(α')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-(α-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-(α-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-(α-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-(α-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'-β-furyl(α')ethenyl-4'-benzopyranylidene)
-benzyl]benzopyrylium perchlorate
46. 2,3-diphenyl-4-[(2'-β-furyl(α')ethenyl-4'-benzopyranylid
ene)benzyl]-6-methylbenzopyrylium perchlorate
47. 2,3-diphenyl-4-[(2'-β-furyl(α')ethenyl-4'-benzopyranylid
ene)methyl]-6-methylbenzopyrylium perchlorate
48. 2-p-methoxystyryl-4-[(2'-β-furyl(α')ethenyl-4'-benzopyra
nylidene)methyl]benzopyrylium perchlorate
49. 2-(α-phenyl-p-methoxystyryl)-4-[(2'-β-furyl(α')eth
enyl-4'-benzopyranylidene)methyl]benzopyrylium perchlorate
50. 9-[(2'-β-furyl(α')ethenyl-4'-benzopyranylidene)methyl]-x
anthylium perchlorate
51. 2-phenyl-4-[(2'-α-phenylstyryl-4'-benzopyranylidene)-benzyl]b
enzopyrylium perchlorate
52. 2-p-methoxystyryl-4-[(2'-α-phenylstyryl-4'-benzopyranylidene)
methyl]benzopyrylium perchlorate
53. 2-(α-phenyl-p-methoxystyryl)-4-[(2'-α-phenylstyryl-4'-b
enzopyranylidene)methyl]benzopyrylium perchlorate
54. 2-phenyl-4-[(2'-α-phenyl-p-methoxystyryl-4'-benzopyranylidene
)benzyl]benzopyrylium perchlorate
55. 2,3-diphenyl-4-[(2'-α-phenyl-p-methoxystyryl-4'-benzopyranyli
dene)benzyl] -6-methylbenzopyrylium perchlorate
56. 2,3-diphenyl-4-[(2'-α-phenyl-p-methoxystyryl-4'-benzopyranyli
dene)methyl]-6-methylbenzopyrylium perchlorate
57. 2-p-methoxystyryl-4-[(2'-α-phenyl-p-methoxystyryl-4'-benzopyr
anylidene)methyl]benzopyrylium perchlorate
58. 2-(α-phenyl-p-methoxystyryl)-4-[(2'-α-phenyl-p-methoxys
tyryl-4'-benzopyranylidene)methyl] benzopyrylium perchlorate
59. 9-[(2'-α-phenyl-p-methoxystyryl-4'-benzopyranylidene)-methyl]
xanthylium perchlorate
60. 2-p-methoxystyryl-4-[(2'-α-phenyl-β-furyl(α')ethen
yl-4'-benzopyranylidene)methyl]benzopyrylium perchlorate
61. 9-[(2'-α-phenyl-β-furyl(α')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-(α-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-(α-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'-β-furyl(α')ethenyl-3'-phenyl-6'-methyl-4
'-benzopyranylidene)benzyl]benzopyrylium perchlorate
75. 2,3-diphenyl-4-[(2'-β-furyl (α')ethenyl-3'-phenyl-6'-met
hyl-4'-benzopyranylidene)benzyl]-6-methylbenzopyrylium
perchlorate
76. 2,3-diphenyl-4-[(2'-β-furyl(α')ethenyl-3'-phenyl-6'-meth
yl-4'-benzopyranylidene)methyl]-6-methylbenzopyrylium perchlorate
77. 2-p-methoxystyryl-4-[(2'-β-furyl(α')ethenyl-3'-phenyl-6'
-methyl-4'-benzopyranylidene)methyl]benzopyrylium perchlorate
78. 2-(α-phenyl-p-methoxystyryl)-4-[(2'-β-furyl(α')eth
enyl-3'-phenyl-6'-methyl-4'-benzopyranylidene)methyl]-benzopyrylium
perchlorate
79. 9-[(2'-β-furyl(α')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-(α-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-(α-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylide
ne)methyl]benzopyrylium fluoborate
89. 2-(α-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylide
ne)methyl]benzopyrylium chloroferrate
90. 2-(α-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'-β-furyl(α')ethenyl-4'-benzopyranylidene)methyl]-b
enzopyrylium perchlorate
107. 2-[(2'-β-furyl(α')ethenyl-4'-benzopyranylidene)methyl]-3
-phenylbenzopyrylium perchlorate
108. 2-[(2'-α-phenylstyryl-4'-benzopyranylidene)methyl]-benzopyryl
ium perchlorate
109. 2-[(2'-α-phenylstyryl-4'-benzopyranylidene)methyl]-3-phenylbe
nzopyrylium perchlorate
110. 2-[(2'-α-phenyl-p-methoxystyryl-4'-benzopyranylidene)-methyl]
benzopyrylium perchlorate
111. 2-[(2'-α-phenyl-p-methoxystyryl-4'-benzopyranylidene)-methyl]
-3-phenylbenzopyrylium perchlorate
112. 2-[(2'-α-phenyl-β-furyl(α')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'-β-furyl(α')ethenyl-3'-phenyl-6'-methyl-4'-benzopy
ranylidene)methyl]benzopyrylium perchlorate
120. 2-[(2'-β-furyl(α')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'-α-phenyl-p-methoxystyryl-4'-benzopyranylidene)-methyl]
-4-p-methoxyphenylbenzothiopyrylium perchlorate
126. 2-[(2'-α-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 (mμ)
______________________________________
1 135˜139
415 and 710
2 130˜132
430 and 720
3 182˜187
410 and 630
4 164˜170
635
5 163˜172
490 and 575
6 >300 575 and 660
7 162˜169
500 and 610
8 180˜187
490 and 670
9 157˜160
550 and 670
10 103˜105
610
11 120˜126
595
12 176˜180
430 and 700
13 122˜126
420 and 730
14 163˜170
420 and 650
15 160˜164
500 and 600
16 166˜169
495 and 710
17 135˜140
580
18 159˜162
555
19 179˜181
420 and 730
20 140˜142
415 and 730
21 165˜172
410 and 700
22 174˜178
500 and 600
23 176˜179
485
24 170˜175
505
25 >300 630
26 >300 560
27 191˜197
560
28 201˜203
500 and 590
29 200˜204
660 and 710
30 185˜189
410 and 650
31 178˜183
430 and 690
32 181˜188
420 and 700
33 117˜123
550 and 650
34 185˜189
590
35 159˜164
495 and 600
36 185˜188
610, 650 and 700
37 160˜165
415 and 650
38 204˜206
425 and 700
39 166˜169
415 and 730
40 >300 660
41 173˜180
555
42 175˜181
540 and 600
43 167˜173
660 and 710
44 161˜164
580 and 720
45 145˜150
415 and 720
46 188˜190
425 and 720
47 168˜175
670
48 171˜176
490 and 580
49 179˜186
600 and 720
50 171˜175
610 and 660
51 151˜155
480 and 740
52 171˜176
495 and 580
53 173˜177
590 and 700
54 140˜147
550 and 750
55 203˜207
420 and 680
56 138˜ 142
555 and 680
57 170˜175
570
58 154˜157
585 and 690
59 168˜174
570
60 206˜209
600
61 >300 650
62 139˜146
550
63 202˜204
425 and 700
64 173˜177
530 and 690
65 190˜194
590
66 190˜193
500 and 600
67 192˜195
620
68 112˜118
570 and 760
69 190˜192
495
70 154˜159
650 and 700
71 177˜182
500 and 710
72 176˜181
590
73 195˜199
495 and 640
74 189˜195
550
75 184˜187
415 and 720
76 192˜196
640 and 700
77 >300 550
78 219˜222
550
79 226˜230
630
80 127˜134
410 and 745
81 190˜192
425 and 730
82 156˜159
665
83 164˜169
600 and 680
84 175˜ 178
600 and 720
85 170˜177
550 and 700
86 157˜166
650 and 695
87 169˜172
635
88 137˜140
500 and 610
89 167˜172
500 and 610
90 160˜163
500 and 610
91 >300 575
92 128˜134
575 and 675
93 133˜136
575 and 675
94 152˜158
575 and 675
95 133˜138
575
96 190˜195
575
97 156˜158
620 and 690
98 225˜229
565
99 183˜187
525 and 560
100 208˜212
570
101 170˜176
630 and 690
102 225˜228
610
103 163˜168
610 and 690
104 178˜184
510
105 172˜175
580 and 690
106 167˜171
565 and 620
107 190˜194
560 and 635
108 211˜214
570 and 610
109 175˜179
570 and 610
110 198˜201
570 and 610
111 158˜163
580 and 630
112 >300 600 and 645
113 185˜188
570 and 620
114 199˜204
600
115 211˜215
565 and 600
116 177˜181
570 and 610
117 205˜207
570
118 190˜194
590
119 237˜241
560
120 >300 590
121 207˜210
565 and 605
122 155˜158
615 and 675
123 143˜145
615
124 126˜131
619
125 144˜148
559 and 657
126 140˜142
589 and 663
127 149˜153
656
128 141˜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° to 139° C.
(b) 2-(α-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)methyl]benzopyrylium perchlorate (compound number 7) ##SPC9##
5.5 grams of 2-(α-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° to 169°C. In the procedure above mentioned the solution ios poured into an ether solution of BF3.O(C2 H5)2 instead of 10 weight percent perchloric acid. In this case 2-(α-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)methyl]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-(α-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)-methyl]benzopyrylium chlorozincate (compound number 90) is obtained.
(c) 2-p-methoxystyryl-3-phenyl-4-[(2'-styryl-4'-benzopyranylidene)methyl]-6-methylbenzopyrylium perchlorate (compound number 18) ##SPC10##
2-styryl-4-methoxybenzopyrylium o-nitrobenzenesulfon (melting point, 155° to 157° C) is obtained by a reaction of 2-styrylchromone and methyl o-nitrobenzenesulfonate in dry benzene at 50° 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-methylbenzopyrylium perchlorate crystals which have a color of reddish violet in dichloroethane and have a melting point of 159° to 162° C. The product is obtained in 73% yield.
(d) 2-(α-phenyl-p-methoxystyryl)-4-[(4'-benzopyranylidene)-methyl]benzopyrylium perchlorate (compound number 22) ##SPC11##
4-methoxybenzopyrylium o-nitrobenzenesulfonate reacts with 2-(α-phenyl-p-methoxystyryl)-4-methyl]benzopyrylium perchlorate to 2-(α-phenyl-p-methoxystyryl)-4-[(4'-benzopyranylidene)methyl]-benzopyrylium perchlorate in the same procedure as the procedure (a). The crystals have a color of violet in dichloroethane and a melting point of 174° to 178°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° to 213°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°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° to 181°C.
(f) 2-(α-phenyl-p-methoxystyryl)-4-(2'-p-methoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranylidene)methyl]-benzopyrylium perchlorate (compound number 66) ##SPC13##
2-p-Methoxystyryl-3-phenyl-4-methoxy-6-methylbenzopyrylium o-nitrobenzenesulfonate (melting point 141° to 144°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-(α-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° to 193° 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° to 177° 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° 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° to 134° 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-phenylbenzopyrylium perchlorate (compound number 11) ##SPC16##
2-(α-Phenyl-p-methoxystyryl)-4-methoxybenzopyrylium o-nitrobenzenesulfonate, which is obtained from 2-(α-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° to 163°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°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°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.
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 7μ 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
______________________________________
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 10μ 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.
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 14μ 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.
Claims (16)
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##
R1 is hydrogen, phenyl or an ethenyl radical selected from the group consisting of styryl, p-methoxystyryl, 3,4-dimethoxy-styryl, α-phenylstyryl, α-phenyl-p-methoxystyryl, β-furyl(α')ethenyl and α-phenyl-β-furyl(α') ethenyl;
R2 is hydrogen or phenyl;
R3 is hydrogen, methyl or phenyl;
R4 is hydrogen or phenyl;
R5 is hydrogen, phenyl or an ethenyl radical selected from the group consisting of styryl, p-methoxystyryl, 3,4-dimethoxy-styryl, α-phenyl-p-methoxystyryl, β-furyl(α')ethenyl and α-phenyl-β-furyl(α')ethenyl;
R6 is hydrogen or phenyl;
R7 is hydrogen or phenyl; .Iadd.
R8 is hydrogen or phenyl;
R9 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-(α-phenyl-p-methoxystyryl)-4-[(2'-phenyl-4'-benzopyranylidene)methyl]benzopyrylium perchlorate, 2-p-methoxystyryl-4-[(2'-3",4"-dimethoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranylidene)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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/495,520 USRE28698E (en) | 1970-03-13 | 1974-08-07 | Electrophotographic material containing sensitizers |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2176670A JPS4843151B1 (en) | 1970-03-13 | 1970-03-13 | |
| JA45-21766 | 1970-03-13 | ||
| JA45-21767 | 1970-03-13 | ||
| JP2176770A JPS4843152B1 (en) | 1970-03-13 | 1970-03-13 | |
| US12150871A | 1971-03-05 | 1971-03-05 | |
| US05/495,520 USRE28698E (en) | 1970-03-13 | 1974-08-07 | Electrophotographic material containing sensitizers |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US12150871A Reissue | 1970-03-13 | 1971-03-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE28698E true USRE28698E (en) | 1976-01-27 |
Family
ID=27457633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/495,520 Expired - Lifetime USRE28698E (en) | 1970-03-13 | 1974-08-07 | Electrophotographic material containing sensitizers |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE28698E (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002238A1 (en) * | 1977-11-28 | 1979-06-13 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Electrophotographic elements and method for their preparation |
| US4173473A (en) | 1977-07-06 | 1979-11-06 | Eastman Kodak Company | Radiation sensitive compositions containing pyrylium compounds |
| US4985323A (en) * | 1987-09-29 | 1991-01-15 | Fuji Photo Film Co., Ltd. | Electrophotographic printing plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3526502A (en) * | 1966-07-18 | 1970-09-01 | Matsushita Electric Ind Co Ltd | Electrophotographic material |
| US3586500A (en) * | 1968-11-01 | 1971-06-22 | Eastman Kodak Co | Electrophotographic composition and element |
| US3617268A (en) * | 1969-01-30 | 1971-11-02 | Matsushita Electric Ind Co Ltd | Electrophotographic materials |
-
1974
- 1974-08-07 US US05/495,520 patent/USRE28698E/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3526502A (en) * | 1966-07-18 | 1970-09-01 | Matsushita Electric Ind Co Ltd | Electrophotographic material |
| US3586500A (en) * | 1968-11-01 | 1971-06-22 | Eastman Kodak Co | Electrophotographic composition and element |
| US3617268A (en) * | 1969-01-30 | 1971-11-02 | Matsushita Electric Ind Co Ltd | Electrophotographic materials |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4173473A (en) | 1977-07-06 | 1979-11-06 | Eastman Kodak Company | Radiation sensitive compositions containing pyrylium compounds |
| EP0002238A1 (en) * | 1977-11-28 | 1979-06-13 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Electrophotographic elements and method for their preparation |
| US4985323A (en) * | 1987-09-29 | 1991-01-15 | Fuji Photo Film Co., Ltd. | Electrophotographic printing plate |
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