U.S. patent number 3,798,031 [Application Number 05/304,939] was granted by the patent office on 1974-03-19 for photoconductive 1,2,3,4-tetrahydroquinolines employed in electrophotography.
This patent grant is currently assigned to Agfa-Gevaert N.V.. Invention is credited to Jozef Aime Dierckx, Wilhelmus Janssens, Robert Joseph Pollet, Hendrik Hubert Sneyers, Johannes Josephus Vanheertum.
United States Patent |
3,798,031 |
Janssens , et al. |
March 19, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
PHOTOCONDUCTIVE 1,2,3,4-TETRAHYDROQUINOLINES EMPLOYED IN
ELECTROPHOTOGRAPHY
Abstract
Electrophotographical recording process wherein a pattern of
increased conductivity is produced image-wise in a photoconductive
insulating recording layer containing as essential photoconductive
compound a photoconductive 1,2,3,4-tetrahydroquinoline. The
photoconductive compound can be chemically and spectrally
sensitized and charged either negatively or positively.
Inventors: |
Janssens; Wilhelmus (Aarschot,
BE), Vanheertum; Johannes Josephus (Halle-Zandhoven,
BE), Pollet; Robert Joseph (Vremde, BE),
Sneyers; Hendrik Hubert (Wijnegem, BE), Dierckx;
Jozef Aime (Mechelen, BE) |
Assignee: |
Agfa-Gevaert N.V. (Mortsel,
BE)
|
Family
ID: |
10463351 |
Appl.
No.: |
05/304,939 |
Filed: |
November 9, 1972 |
Foreign Application Priority Data
|
|
|
|
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Nov 10, 1971 [GB] |
|
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52287/71 |
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Current U.S.
Class: |
430/63; 430/76;
430/77; 430/79; 544/135; 544/296; 546/77; 546/178; 548/121;
548/159; 548/455; 549/320; 252/501.1; 430/78; 430/88; 544/143;
546/62; 546/152; 546/181; 548/156; 548/472 |
Current CPC
Class: |
C07D
215/20 (20130101); C07D 221/18 (20130101); C07D
215/06 (20130101); G03G 5/0637 (20130101); G03G
5/0661 (20130101); C07D 455/04 (20130101); G03G
5/0646 (20130101) |
Current International
Class: |
C07D
215/06 (20060101); C07D 215/00 (20060101); C07D
221/18 (20060101); C07D 215/20 (20060101); C07D
221/00 (20060101); C07D 455/04 (20060101); C07D
455/00 (20060101); G03G 5/06 (20060101); G03g
005/06 () |
Field of
Search: |
;96/1.5,1PC,1.8
;252/501 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1,245,924 |
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Sep 1971 |
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GB |
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1,588,977 |
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Apr 1970 |
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FR |
|
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Miller; John R.
Attorney, Agent or Firm: Daniel; William J.
Claims
We claim:
1. In a recording process wherein a photoconductive insulating
recording layer is exposed to an electromagnetic radiation image to
produce an imagewise pattern of increased conductivity in said
photoconductive recording element and said conductivity pattern is
developed to produce a record of said image, the improvement
wherein said element comprises an organic photoconductive compound
corresponding to the following general formula: ##SPC30##
wherein:
z.sub.1 represents the necessary atoms to close an adjacent
aromatic nucleus or an adjacent aromatic ring system including such
a nucleus or ring system substituted with one or more substituents
having a non-ionic character,
R.sub.1 represents hydrogen, an aliphatic radical, or an alkylene
group which is ring closed with the carbon atom in peri-position of
the aromatic ring closed by Z.sub.1, and R.sub.2 represents
hydrogen or a lower alkyl group.
2. A recording process according to claim 1, wherein R.sub.1
represents an alkyl radical introduced by alkylation.
3. A recording process according to claim 1, wherein Z.sub.1
represents the necessary atoms to close an adjacent benzene
nucleus.
4. A recording process according to claim 1, wherein each R.sub.2
represents a methyl group.
5. A recording to claim 1, wherein the photoconductive compound
corresponds to the following general formula: ##SPC31##
wherein :
Z.sub.1 represents the necessary atoms to close an adjacent
aromatic nucleus or an adjacent aromatic ring system including such
a nucleus or ring system substituted with one or more substituents
having a non-ionic character, A represents an alkylene group, or an
alkylene chain interrupted by a bivalent aromatic group, and
R.sub.2 represents hydrogen or a lower alkyl group.
6. A method for recording and reproducing information comprising
the steps of producing an electrostatic charge pattern by
electrostatically charging and information-wise exposing to
electromagnetic radiation a recording element containing a
photoconductive compound corresponding to the following general
formula: ##SPC32##
wherein:
Z.sub.1 represents the necessary atoms to close an adjacent
aromatic nucleus or an adjacent aromatic ring system including such
a nucleus or ring system substituted with one or more substituents
having a non-ionic character,
R.sub.1 represents hydrogen, an aliphatic radical, or an alkylene
group which is ring closed with the carbon atom in peri-position of
the aromatic ring closed by Z.sub.1, and
R.sub.2 represents hydrogen or a lower alkyl group, producing
thereby an information-wise increase of the conductivity in the
recording element, and developing the resulting latent
electrostatic charge pattern with a substance that can be
electrostatically attracted.
7. A process according to claim 1, wherein the recording element is
a recording layer that has been applied to an electro conductive
layer or support having a resistivity lower than that of the
dark-adapted recording element.
8. A process according to claim 7, wherein the electro conductive
layer or support has a resistivity at least 10.sup.2 as low as that
of the recording element in the dark.
9. A process according to claim 7, wherein the support is a paper
support.
10. A process according to claim 7, wherein the support is an
insulating transparent resin support coated with a transparent
electroconductive interlayer.
11. A process according to claim 10, wherein said interlayer
contains a polyionic resin.
12. A process according to claim 1, wherein the photoconductive
compound is used in admixture with a polymeric binding agent.
13. A process according to claim 1, wherein the photoconductive
compound is used in admixture with a halogen-containing polymer, an
epoxy resin and/or silicone resin.
14. A process according to claim 13, wherein the halogen-containing
polymer contains vinyl chloride units.
15. A process according to claim 1, wherein the photoconductive
compound is used in admixture with a substance increasing the
photosensitivity of the recording element.
16. A process according to claim 1, wherein the photoconductive
compound is used in admixture with a spectral sensitizing dye.
17. A process according to claim 1, wherein the defined organic
photoconductive compound is used in admixture with (an) other
inorganic and/or organic photoconductive substance(s).
18. A recording material containing a photoconductive insulating
recording element capable of being electrostatically charged in the
absence of active electromagnetic radiation and capable of
retaining the applied charge for a period of time long enough to
produce thereon a developed electrostatic charge pattern,
characterized in that the recording element stands in
electroconductive relationship to a layer or support with a lower
resistivity than that of the recording element and in that the
recording element contains an organic photoconductive compound
corresponding to the following general formula: ##SPC33##
wherein :
Z.sub.1 represents the necessary atoms to close an adjacent
aromatic nucleus or an adjacent aromatic ring system including such
a nucleus or ring system substituted with one or more substituents
having a non-ionic character,
R.sub.1 represents hydrogen, an aliphatic radical or an alkylene
group which is ring closed with the carbon atom in peri position of
the aromatic ring closed by Z.sub.1, and
R.sub.2 represents hydrogen or a lower alkyl group.
19. A recording material according to claim 18, wherein R.sub.1
represents an alkyl radical introduced by alkylation.
20. A recording material according to claim 18, wherein Z.sub.1
represents the necessary atoms to close an adjacent benzene
nucleus.
21. A recording material according to claim 18, each R.sub.2
represents a methyl group.
22. A recording material according to claim 18, wherein the
photoconductive compound corresponds to the following general
formula: ##SPC34##
wherein :
Z.sub.1 represents the necessary atoms to close an adjacent
aromatic nucleus or an adjacent aromatic ring system including such
a nucleus or ring system substituted with one or more substituents
having a non-ionic character, A represents an alkylene group, or an
alkylene chain interrupted by a bivalent aromatic group, and
R.sub.2 represents hydrogen or a lower alkyl group.
23. A recording material according to claim 22, wherein Z.sub.1
represents the necessary atoms to cloSe an adjacent benzene nucleus
or adjacent benzene nucleus substituted with methyl or alkoxy, and
A represents an alkylene group, a substituted alkylene group or an
alkylene chain interrupted by a bivalent aromatic group.
24. A recording material according to claim 18, each R.sub.2
represents a methyl group.
25. A recording material according to claim 18, wherein the
recording element is a supported or self-supported layer.
26. A recording material according to claim 18, wherein the
recording element contains said organic photoconductive compound in
an amount of at least 5 percent by weight.
27. A recording material according to claim 18, wherein the
recording element is in layer or sheet form and stands in
electroconductive contact with a layer or support that has a
resistivity being at least 10.sup.2 times as low as that of the
recording element in the dark.
28. A recording material according to claim 18, wherein the support
is a paper support.
29. A recording material according to claim 18, wherein the support
is an insulating transparent resin support coated with a
transparent electroconductive interlayer.
30. A recording material according to claim 29, wherein said
interlayer contains a polyionic resin.
31. A recording material according to claim 18, wherein the organic
photoconductive compound is used in admixture with a polymeric
binding agent.
32. A recording material according to claim 31, wherein the
photoconductive compound is used in admixture with a
halogen-containing polymer, epoxy resin and/or silicone resin.
33. A recording material according to claim 18, wherein the organic
photoconductive compound is used in admixture with a spectral
sensitizing dye.
34. A recording material according to claim 18, wherein the organic
photoconductive compound is used in admixture with (an) other
inorganic and/or other organic photoconductive substance(s).
35. A recording material according to claim 34, wherein the organic
photoconductive compound is used in admixture with a
photoconductive compound selected from the group of photoconductive
selenium and the photoconductive oxides, sulphides and selenides of
zinc, cadmium, mercury, antimony, bismuth and lead.
36. A recording material according to claim 18, wherein the
photoconductive recording element has an optical density not higher
than 0.30 for visible light or copying light.
37. A recording material according to claim 33, wherein the
recording element contains a spectrally sensitizing triarylmethane
dye, xanthene dye and/or methine dye.
38. A recording material according to claim 18, wherein the
recording element contains as chemical sensitizing agent a compound
having (a) substituent(s) with srong electron-attracting
(electro-negative) character.
39. A recording material according to claim 38, wherein the
chemical sensitizing agent is a non-ionic Lewis acid compound.
40. A recording material according to claim 39, wherein the
chemical sensitizing agent is a quinone, which is substituted with
halogen or cyano.
Description
This invention relates to recording and reproduction of
information-wise modulated electromagnetic radiation and to
recording materials suitable therefor, particularly to such
processes and recording materials containing one or more organic
photoconductive compounds as hereinafter described.
It has now been found that a particularly photosensitive
photoconductive recording member can be formed by using in its
composition a photoconductive compound corresponding to the
following general formula (I) : ##SPC1##
wherein:
Z.sub.1 represents the necessary atoms to close an adjacent
aromatic nucleus or an adjacent aromatic ring system including an
adjacent aromatic nucleus or aromatic ring system substituted with
(a) non-ionic substituent(s) e.g. substituted with an alkyl group
for example methyl, halogen e.g. F, Cl, Br or I, an alkoxy group
e.g. methoxy, an amino group, a substituted amino group e.g. a
monoalkylamino or dialkylamino group or a cyano group,
Z.sub.2 represents the necessary methylene groups or substituted
methylene groups to close a 6-membered heterocyclic
nitrogen-containing nucleus. Suitable substituents for the
methylene groups are one or more C.sub.1 -C.sub.4 alkyl groups e.g.
methyl, and
R represents hydrogen, an aliphatic radical including a saturated
aliphatic radical, an unsaturated aliphatic radical, a
cyclo-aliphatic radical and these radicals in substituted form, or
an alkylene group which is ring-closed with the carbon atom in
peri-position of the aromatic ring closed by Z.sub.1 in order to
form a julolidine compound.
According to a preferred embodiment R represents an organic group
that can be introduced by alkylation, for example an alkyl radical
including a substituted alkyl radical, e.g. methyl, a cycloalkyl
radical, e.g. cyclohexyl, an allyl radical, an aralkyl radical,
e.g. benzyl.
The adjacent aromatic nucleus or ring system closed by the atoms
represented by Z.sub.1 is preferably one of the unsubstituted or
substituted nuclei or ring systems represented by the following
structural formulae: ##SPC2##
Wherein R represents hydrogen or an alkyl group e.g. methyl or
ethyl ##SPC3##
Wherein R represents hydrogen or an alkyl group, e.g. methyl or
ethyl. ##SPC4##
Wherein : X represents oxygen or sulphur ##SPC5##
Wherein : X represents oxygen or sulphur ##SPC6##
wherein : X represents oxygen or sulphur, and R represents hydrogen
or an alkyl group, e.g. methyl or ethyl. ##SPC7##
wherein : R is hydrogen or an alkyl group, e.g. methyl or
ethyl.
Preferred photoconductive compounds according to the present
invention and which are considered as new compounds are within the
scope of the following general formula (II) : ##SPC8##
wherein :
Z.sub.1 and Z.sub.2 have the same significance as described in the
above general formula, and A represents a bivalent organic radical
of the type that can be introduced by alkylation, e.g. A represents
an alkylene group, a substituted alkylene group or an alkylene
chain interrupted by a bivalent aromatic group. Preferably A
represents -CH.sub.2 -CH.sub.2 - or ##SPC9##
Particular examples of photoconductive compounds according to the
general formula (I) are listed in the following Table I. ##SPC10##
##SPC11##
Particularly useful photoconductive compounds according to the
general formula (II) are listed in the following Table II. These
compounds are called "duplo compounds" for they include two
1,2,3,4-tetrahydroquinoline nuclei. ##SPC12## ##SPC13##
The preparation of the compounds according to the formula of Table
I proceeds by hydrogenation of the corresponding
1,2-di-hydroquinoline compounds which are prepared e.g. according
to a procedure described in the Belgian Pat. Specification Nos.
775,786 filed Nov. 25, 1971 and 776,380 filed Dec. 8, 1971 both by
Agfa-Gevaert N.V.
The substitution of the hydrogen atom in the NH group of the
Z.sub.2 -ring by an organic group may proceed according to known
alkylating techniques. This alkylation may be carried out before or
after the hydrogenation of the double bond between the three- and
four-carbon atom in the 1,2-dihydroquinoline compound.
For introducing an alkyl substituent by substitution of the
hydrogen atom of said NH group any suitable alkylating agent e.g.
trialkyl phosphate, alkyl iodides, alkyl bromides and alkyl
chlorides may be used, the latter preferably in conjunction with a
small amount of potassium iodide.
The preparation of the "duplo-compounds" as e.g. represented in
Table II proceeds by linking together two
1,2,3,4-tetrahydro-quinolines by alkylation through the nitrogen
atoms in the 1-position.
As suitable bifunctional alkylating agents are to be mentioned
dihalogenated reactants of the formula Hal-A-Hal in which Hal
represents a replaceable halogen atom e.g. chlorine, bromine or
iodine and A has the same significance as described above.
The following are illustrative of reactants that may be used in the
preparation of the duplo-compounds :
ethylene dichloride, dibromide and diiodide
1-chloro-2-bromoethane
propylene dichloride, dibromide and diiodide
trimethylene dichloride, dibromide and bromoiodide
butylene dichloride, dibromide and diiodide
tetramethylene dichloride, dibromide and diiodide
pentylene dichloride, dibromide and diiodide
hexamethylene dichloride dibromide and diiodide
hexylene dichloride, dibromide and diiodide
octylene dichloride, dibromide and diiodide
pentamethylene dichloride, dibromide and diiodide
alpha, beta-styrene dichloride, dibromide and diiodide
1,2-dibromocyclohexane
1,3-dibromobutane
1,2-dibromobutane
1,4-dichlorobutene-2
2-phenyl-1,2-dibromopropane
1-p-tolyl-1,2-dichloroethane
1,4-di(chloromethyl)benzene
1,4-di(bromomethyl)benzene
1,4-di(iodomethyl)benzene
1-(2,4-dichlorophenyl)-1,2-dichloroethane
1-(p-chlorophenyl)-1,2-dibromoethane
decamethylene dichloride, dibromide and diiodide
dodecamethylene dichloride, dibromide and diiodide
1,2-dibromobutene-3
1,2-dichloropentene-4
1,2-dichloro-3-methylbutene-3
1,4-dichlorobutene-2
1,4-dibromo-2,3-dimethylbutene-2
1,2-dichlorocyclopentene-3
1,4-dibromocyclopentene-2
1,4-dibromo-2,6-dimethylheptene-2
2,3-dichloro-2,6-dimethyloctene-6
Other suitable reactants for the duplo-compound formation are the
.beta.-chloroethyl ester of p-tolusulphonic acid and the
p-tolusulphonic acid glycol diester.
Preferred reactants are sym.-dibromoethane and
sym.-dichloroethane.
The acid produced during the alkylation reaction may be neutralized
by any alkaline neutralizing agent ordinarily employed for
neutralizing acids produced in condensation reactions e.g. an
organic base.
The following preparations illustrate in more details the
manufacture of the compounds enumerated in the Tables I and II.
PREPARATION OF COMPOUND 5 OF TABLE I
0.1 mole of the corresponding 1,2,3,4-tetrahydroquinoline was mixed
with 0.3 mole of benzyl chloride in the presence of 0.12 mole of
anhydrous sodium carbonate in 150 ml of ethanol. The reaction
mixture was refluxed for 6 h whereupon it was filtered. The solvent
was removed from the filtrate by evaporation. The residue was
washed with cold methanol and distilled under reduced pressure. The
fraction boiling between 145.degree. C and 149.degree. C at 0.2 mm
Hg was collected.
Compound 1 of Table I was prepared analogously.
Compounds 8 and 9 were recrystallized from acetonitrile.
PREPARATION OF COMPOUND 2 OF TABLE I
0.2 mole of the corresponding 1,2-dihydroquinoline and 4 ml of a
dispersion of Raney nickel were mixed with 150 ml of dioxan.
Hydrogen pressure of 1,500 psi was applied and the hydrogenation
effected at 70.degree. C for 2 h. The measured hydrogen acception
corresponded with the theoretically possible value. After removal
by filtering of the Raney nickel the solvent was removed by
evaporation and the residue distilled under reduced pressure with
the help of a fractionating column. The fraction boiling between
105.degree.-106.degree. C at 0.5 mm Hg was collected.
Compounds 3 and 10 of Table I were prepared analogously.
Compound 10 was not distilled but recrystallized from ligroin in
the presence of active carbon.
PREPARATION OF COMPOUND 4 OF TABLE I
A mixture of 0.2 mole of 1,2,3,4-tetrahydroquinoline, 0.4 mole of
trimethyl phosphate and 0.21 mole of ethyl diisopropylamine were
heated at 140.degree. C on an oil-nath for 1 h.
The reaction mixture was poured into water and treated with
sufficient ammonium hydroxide for obtaining a slightly alkaline
reaction.
The obtained supernatent oily product was extracted with
chloroform. The whole mixture was washed with 2N aqueous
hydrochloric acid and thereupon washed with water until neutral.
After drying on anhydrous sodium sulphate the extract was distilled
under reduced pressure with a distillation column and the fraction
boiling between 130.degree.-132.degree. C at 15 mm Hg
collected.
PREPARATION OF COMPOUND 6 OF TABLE I
90.5 g of the corresponding 1,2-dihydroquinoline were hydrogenated
in the presence of Raney nickel under 1,500 psi of hydrogen
pressure at 70.degree. C in dioxan as a solvent. After removal of
the Raney nickel by filtering the solvent was evaporated under
reduced pressure and the hydrogenated product purified by
distillation. The fraction boiling between 148.degree.-151.degree.
C at 3 mm Hg was collected.
PREPARATION OF COMPOUNDS 1, 3, 4 and 5 OF TABLE II
The hydrogenation of the corresponding 1,2-dihydroquinoline to the
indicated 1,2,3,4-tetrahydroquinoline of Table II proceeded in a
total liquid volume of 300 ml by using 0.1 mole of the
1,2-dihydroquinoline, 3 ml of Raney nickel dispersion and the
balance of dioxan at 1,500 psi. The hydrogenation was effected at
85.degree. C for 2 h. The hydrogen acceptance was slightly more
than the theoretical value. After removal of the Raney nickel by
filtering the solvent was evaporated.
Compound 1 was recrystallized from acetonitrile, compound 3 from
butanol and compounds 4 and 5 from ethanol.
PREPARATION OF COMPOUND 2 OF TABLE II
The alkylation was carried out by heating with stirring 0.2 mole of
the 1,2,3,4-tetrahydroquinoline with 0.1 mole of sym.-dibromoethane
and 0.2 mole of triisopropanolamine at 100.degree. C for 10 h. The
obtained reaction product was extracted with dichloroethane and
washed first with 2N aqueous hydrogen chloride and then with water
until neutral.
The extract was dried over anhydrous sodium sulphate and after
filtering the solvent was removed. Recrystallization of the crude
product from ethylene glycol monomethyl ether yielded a white
powder.
Melting point : 151.degree. C. Yield : 54 percent.
In the preparation of the compounds 6 and 7 of Table II
1,4-di(monochloromethyl)benzene was used instead of
sym.-dibromoethane.
The photoconductive duplo compounds of Table II are particularly
interesting for their high photosensitivity and pure state wherein
they can be separated. Most of these products are obtained as white
powders, which are suited for producing very clear colourless
photosensitive layers.
The photoconductive compounds applied according to the present
invention may be used alone or in combination with substances
imparting desired chemical or physical properties to the recording
element. So, these substances may be combined with other substances
that either or not are photoconductive and exert an influence e.g.
on the dark-resistivity, the dischargeability of conductivity of
the recording layer by an exposure to electromagnetic radiation, or
on the transparency or the quality of the final image, e.g. by
counteracting the fringe effect as described in the United Kingdom
Pat. specification No. 1,007,349 filed Oct. 12, 1961 by Gevaert
Photo-Producten N.V.
A proper combination with selected binding agents and/or chemical
sensitizing agents may result in an enhancement of the total
sensitivity. The recording elements according to the present
invention preferably contain at least 5 percent by weight of a
photoconductive 1,2,3,4-tetrahydroquinoline derivative being within
the scope of the above general formulae. For use in
electrophotography the recording element preferably consists for at
least 10 percent by weight of one or more of the said
1,2,3,4tetrahydroquinoline derivatives. The electrically insulating
binding agent used in a recording layer containing said derivative
may provide the desired mechanical strength for instance to form a
self-supporting layer, and preferably has a resistivity of at least
10.sup.9 ohm.cm.
According to a particular embodiment the recording layer consists
of the photoconductor, which, e.g., has been applied to a suitable
support in molten state forming a micro-crystalline or glass-like
layer on cooling. This technique can be applied when the
photoconductive recording element has not to possess a high
mechanical strength. For such technique reference is made to the
Canadian Pat. specification No. 712,541 filed Feb. 5, 1960 by
Gevaert Photo-Producten N.V.
Macromolecular compounds suitable for use as insulating binding
agent for the photo-conductive compounds are, e.g., natural resins
such as dammar resin, gum arabic, microcrystalline waxes, modified
natural substances such as cellulose diacetate, cellulose
triacetate, and ethylcellulose, pentaerythrite polyesters or
modified colophony resins and ester gums, polymers such as
polyethylene, polystyrene and copolymers of styrene, polyvinyl
acetate and copolymers of vinyl acetate, polyvinyl acetals of
formaldehyde, acetaldehyde or butyraldehyde, polyacrylic acid
esters and polymethacrylic acid esters, coumarine-indene resins,
epoxy resins and polycondensates such as glycerol-phthalate resins
and other glyceryl polyesters, alkyd resins, diethylene glycol
polyesters, formaldehyde resins and silicone resins.
Preferred binding agents are halogen-containing polymers and epoxy
resins combined with silicone resins. The sensitization of organic
photoconductors with halogen-containing polymers is described in
the United Kingdom Pat. specification No. 964,878 filed May 3, 1960
by Gevaert Photo-Producten N.V. According to said specification a
material suitable for use in electrophotography comprises a
photoconductive layer incorporating an organic monomeric
photoconductor and a halogen-containing polymer in such layer or in
a juxtaposed layer (if any), the sensitivity of said photoconductor
having been increased by making it to interact with said
halogen-containing polymer by heating.
In the following Table III a list of preferred polymeric binding
agents is given, which may be used in combination with the
heterocyclic organic photoconductors of use according to the
present invention as well as the corresponding suitable solvents.
##SPC14##
According to a special embodiment the photoconductive compounds
applied according to the present invention are used in admixture
with inorganic and organic photoconductive substances known to
those skilled in the art, e.g. sulphur, selenium, photoconductive
oxides, sulphides, and selenides of zinc, cadmium, mercury,
antimony, bismuth, lead, anthracene, anthraquinone, and
photoconductive polymers e.g. those containing N-vinylcarbazole
recurring units and other known monomeric and polymeric organic
photoconductors, e.g. those described in the published Dutch Pat.
application No. 70/04174 filed Mar. 24, 1970 by Gevaert-Agfa
N.V.
The inherent spectral sensitivity of most of the photoconductive
compounds listed in Tables I and II is mainly situated in the near
U.V. range, i.e., in the range of 360 to 420 nm.
The spectral sensitivity of recording materials according to the
present invention can be increased in different ways, e.g. by
adding so-called spectral sensitizing agents for the
photoconductive substances contained in the recording element or by
admixing to the said heterocyclic organic photoconductive compounds
other photoconductive substances, whose inherent sensitivity for a
particular part of the electromagnetic radiation spectrum is higher
than that of the present compounds.
Suitable spectral sensitizing dyestuffs for the organic
photoconductor are among others organic dyestuffs, known as methine
dyes, or xanthene dyes of which the phthaleins and rhodamines are
subclasses, and triarylmethane dyes e.g. crystal violet (C.I.
42,555) and the triarylmethane dyes described in published Dutch
Pat. application No. 6,704,706 filed April 3, 1967 by Gevaert-Agfa
N.V. The term methine dyes includes mono- as well as polymethine
dyes, which dyes are known to those skilled in the art of the
spectral sensitization of light-sensitive silver halide. Preferred
methine dyes are of the cationic type. As preferred xanthene dyes
Rhodamine B (C.I. 45,170), Rose Bengale (C.I. 45,440) and
Fluorescein (C.I. 45,350) are mentioned. The spectral sensitizing
dyes are preferably added to the recording layer composition in a
proportion of 0.01 to 5 percent by weight in respect of the
photoconductive substance(s).
Particularly preferred methine dyes are within the scope of the
following general formulae : ##SPC15##
wherein :
A.sub.1 stands for a dimethine or tetramethine group including a
substituted dimethine or tetramethine group,
n stnads for one or two,
R.sub.1 stands for alkyl including substituted alkyl, an
unsaturated aliphatic group e.g. allyl, aralkyl including
substituted arakyl, aryl including substituted aryl or
cycloalkyl,
R.sub.2 stands for alkyl, aryl including substituted aryl, e.g.
phenyl and phenyl substituted preferably in the p-position by
alkyl, halogen and alkoxy, a 5- or 6-membered heterocycle whose
heteroatom is oxygen, sulphur, selenium or nitrogen such as 2-, 3-,
or 4-pyridyl, 2-furyl, 2-thienyl, etc. including their quaternary
salts,
R.sub.3 stands for hydrogen or has one of the significances given
for R.sub.1,
R.sub.4 stands for hydrogen, alkyl, alkoxy or halogen or together
with R.sub.3 forms an alkylene bridge such as dimethylene and
trimethylene,
each of R.sub.5 and R.sub.6 (the same or different) stands for
hydrogen, alkyl, alkoxy or halogen or together represent the atoms
necessary to complete a fused-on benzene nucleus,
X.sub.1 .sup.- represents an anion e.g. Cl.sup.-, Br.sup.-,
I.sup.-, ClO.sub.4 .sup.-, CH.sub.3 SO.sub.4 .sup.-, or ##SPC16##
but is missing when the R.sub.1 group contains already an anion
(betaine type salt), and
Z represents the atoms necessary to complete a heterocyclic nucleus
of the types used in the production of cyanine dyes e.g. such as
those of the thiazole series, e.g. thiazole, 4-methylthiazole,
4-methyl-5-carbethoxythiazole, 4-phenylthiazole, 5-methylthiazole,
5-phenylthiazole, 4-(p-tolyl)-thiazole, 4-(p-bromophenyl)-thiazole,
4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)-thiazole,
4-(m-nitrophenyl)-thiazole, those of the benzothiazole series, e.g.
benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole,
6-chlorobenzothiazole, 7chlorobenzothiazole, 4-methylbenzothiazole,
5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole,
6-bromobenzothiazole, 6-sulphobenzothiazole, 4-phenylbenzothiazole,
5-phenylbenzothiazole, 4-methoxybenzothiazole,
5-methoxybenzothiazole, 6-methoxybenzothiazole,
5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole,
5-ethoxybenzothiazole, 4,5,6,7-tetrahydrobenzothiazole,
5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole,
5-hydroxybenzothiazole, 6-hydroxybenzothiazole,
5,6-dimethylbenzothiazole, those of the naphthothiazole series e.g.
naphtho[2,1-d]thiazole, naphtho [1,2-d]thiazole,
5-methoxynaphtho[1,2-d]-thiazole, 5-ethoxynaphtho[1,2-d]-thiazole,
3-methoxynaphtho[2,1-d]-thiazole, 7methoxynaphtho[2,1-d]-thiazole,
those of the thionaphtheno[7,6-d]-thiazole series
e.g.7-methoxythionaphtheno[7,6-d]-thiazole, those of the
thiadiazole series e.g. 4-phenylthiadiazole, those of the oxazole
series e.g. 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole,
4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole,
5-phenyloxazole, those of the benzoxazole series e.g. benzoxazole,
5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole,
6-methylbenzoxazole, 5,6-dimethylbenzoxazole,
4,6-dimethylbenzoxazole, 5-methoxybenzoxazole,
6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole,
those of the naphthoxazole series, e.g. naphtho[2,1-d]oxazole,
naphtho[1,2-d]oxazole, those of the selenazole series e.g.
4-methylselenazole, 4-phenylselenazole, those of the
benzoselenazole series e.g. benzoselenazole,
5-chlorobenzoselenazole, 5-methoxybenzoselenazole,
5-methyl-6-methoxybenzoselenazole,
5,6-dioxymethylenebenzoselenazole, 5-hydroxybenzoselenazole,
4,5,6,7-tetrahydrobenzoselenazole, those of the naphthoselenazole
series e.g. naphtho[2,1-d]selenazole, naphtho[2,1-d]selenazole,
those of the thiazoline series e.g. thiazoline, 4-methylthiazoline,
4-hydroxymethyl-4-methylthiazoline,
4,6-bis-hydroxymethylthiazoline, those of the oxazoline series e.g.
oxazoline, those of the selenazoline series e.g. selenazoline,
those of the 2-quinoline series e.g. quinoline, 3-methylquinoline,
5-methylquinoline, 7-methylquinoline, 8-methylquinoline,
6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline,
6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.,
those of the 4-quinoline series e.g. quinoline, 6-methoxyquinoline,
7-methylquinoline, 8-methylquinoline, those of the 1-isoquinoline
series e.g. 1-isoquinoline, 3,4-dihydroisoquinoline, those of the
3-isoquinoline series e.g. 3-isoquinoline, those of the pyrimidine
series, those of the quinoxaline series, those of the quninazoline
series, those of the 1phthalazine series, those of the 2-pyridine
series, e.g. pyridine, 5-methylpyridine, 3-nitropyridine, those of
the 3,3-dialkylindolenine series, e.g. 3,3-dimethylindolenine,
3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc., those
of the benzimidazole series e.g. benzimidazole,
5,6-dichlorobenzimidazole, 5-chlorobenzimidazole,
5,6-dibromobenzimidazole, 5-chloro-6-amino-benzimidazole,
5-chloro-6-bromobenzimidazole, 5-phenylbenzimidazole,
5-fluorobenzimidazole 5,6-difluorobenzimidazole,
5-cyanobenzimidazole, 5,6-dicyanobenzimidazole,
5-chloro-6-cyanobenzimidazole, 5-fluoro-6-cyanobenzimidazole,
5-acetylbenzimidazole, 5-chloro-6-fluorobenzimidazole,
5-carboxybenzimidazole, 7-carboxybenzimidazole,
5-carbethoxybenzimidazole, 7-carbethoxybenzimidazole,
5-sulphamylbenzimidazole, or 5-N-ethylsulphamylbenzimidazole,
5-ethylsulphonylbenzimidazole and
5-trifluoromethylsulphonylbenzimidazole; ##SPC17##
wherein :
A.sub.2 stands for a monomethine or trimethine group including a
substituted monomethine or trimethine group,
each of R'.sub.2 - R'.sub.6 and R".sub.2 - R".sub.6 (the same or
different) has one of the significances given for R.sub.2 -
R.sub.6,
X.sub.2 .sup.- has the same significance as X.sub.1 .sup.-;
##SPC18##
wherein :
each of R'.sub.1 and R".sub.1 (the same or different) has one of
the meanings given for R.sub.1,
X.sub.3 .sup.- has the same meaning as X.sub.1 .sup.-,
A.sub.3 has the same meaning as A.sub.2,
each of m and p (the same or different) stands for one or two,
and
each of Z.sub.1 and Z.sub.2 (the same or different) stands for the
atoms necessary to complete a heterocyclic nucleus of the thiazole,
benzothiazole, naphthothiazole, thionaphtheno[7,6-d]-thiazole,
thiadiazole, oxazole, benzoxazole, naphthoxazole, selenazole,
benzoselenazole, naphthoselenazole, 2-quinoline, 4-quinoline,
pyrimidine, quinoxaline, quinazoline, 2-pyridine,
3,3-dialkylindolenine or of the benzimidazole series;
representative examples of these heterocyclic nuclei can be found
above in the definition of Z in formula I.
The dyestuffs corresponding to the above general formulae can be
prepared according to the methods known by those skilled in the art
of methine dye chemistry.
According to a further embodiment of the invention the recording
material contains one or more substances that increase the
photoconductivity of the recording material in the inherent
spectral sensitivity range of the said heterocyclic organic
photoconductive compounds. As already has been said a binding agent
can act as a sensitizing agent that enhances the total sensitivity
of the recording element. In that respect are to be mentioned
compounds containing one or more electron-attracting atoms or
groups, e.g. those that are known as non-ionic Lewis acids,e.g. the
Lewis acids that can form a "charge transfer complex" as described
e.g. in the U.S. Pat. specification No. 3,408,183 of Joseph Mammino
issued Oct. 29, 1968. Good sensitizing results are obtained with
organic carboxylic acid anhydrides and with quinones containing
electron-attracting substituents, e.g. halogen or cyano, such as in
tetrachlorobenzoquinone and tetracyanobenzoquinone, with organic
compounds containing a ##SPC19## group and with the compounds
according to the structural formula of the Belgian Pat.
specification No. 734,141 filed June 6, 1969 by Gevaert-Agfa N.V.
and the chlorine- and/or cyano-containing polymers of Table
III.
The 1,2,3,4-tetrahydroquinoline derivatives may be used in
admixture with diazonium salts that on exposure to electromagnetic
radiation produce (a) radical(s), which irreversibly increase(s)
the electro-conductivity of a recording layer. Such substances as
well as details about their incorporation into a recording layer
containing an organic photoconductive insulating substance are
described in the United Kingdom Pat. specification No. 964,872
filed Apr. 22, 1959 by Gevaert Photo-Producten N.V. and the U.S.
Pat. specification No. 3,113,022 of Paul Maria Cassiers, Jean Marie
Nys, Jozef Frans Willems and Rene Maurice Hart issued Dec. 3, 1963.
A particularly suitable conductivity-increasing diazonium compound
is p-nitrobenzene-diazonium chloride. The diazonium compounds are
preferably used in an amount of 0.0l to 10 percent by weight in
respect of the present photoconductive heterocyclic organic
compounds.
Other additives well known in the art of preparing photoconductive
coatings for recording purposes may be used, e.g. matting agents,
fluorescing compounds, phosphors, optical brightening agents,
agents controlling the adhesive power of the recording layer,
agents controlling the elasticity, the plasticity and the hardness
of the recording layer, agents controlling the viscosity of the
coating composition, antioxidants, gloss-improving agents, etc.
Transparent and semi-transparent recording materials containing the
photoconductive heterocyclic organic compounds as described
hereinbefore are especially suited for use in recording materials
applied for the production and reproduction of microfilm images.
Microfilm images can be copied in contact or enlarged optically on
recording materials according to the present invention. According
to the type of development, the transparencies obtained (contact
copies and enlargements) can serve as negative or positive
intermediate prints for further printing, e.g. on diazotype
materials.
The semitransparent recording materials according to the present
invention preferably have an optical density not larger than 0.30
towards visible light or the copying light used in the printing
apparatus wherein it is used as intermediate print.
The photoconductive heterocyclic organic compounds described
hereinbefore are further especially suited for being applied in the
manufacture of pigment images wherein the pigments may have the
properties of a fluorescent compound or phosphor.
As is generally known luminescent phosphors are used in screens of
cathode-ray tubes and more particularly in television, X-ray, radar
and oscilloscope screens. It is further known that in colour
television screens phosphors of different colour have to be fixed
on a screen in a particular pattern.
The described photoconductive compounds are successfully used in a
process for the production of colour television screens as
described in the French Pat. specification No. 1,336,499 filed
Sept. 26, 1962 by Comp.Francaise Thomson-Houston. According to the
process described in said specification a pattern of a phosphor on
a screen support is produced by the steps of applying to said
support a coating of an electroconductive material and to said
coating a layer comprising a vaporisable or thermolysable
photoconductive compound optionally incorporated in a vaporisable
or thermolysable binding agent. On said coating an electrostatic
charge pattern corresponding with the pigment pattern to be
produced is formed in an electrophotographic way, and the
electrostatic charge pattern is developed with non-volatile powder
particles that have the desired phosphorescent or luminescent
properties. Subsequently the photoconductive layer containing the
phosphor powder image is heated in order to remove the volatile
substances of the photoconductive recording layer and to make the
phosphor pattern adhere to the screen support.
In order to fix the powder image before applying the heating step
it is preferably overcoated with a layer of a thermolysable binding
agent.
According to said French Patent Specification photoconductors of
the group of anthracene, anthraquinone and xanthene are used. The
recording layer may further contain boric acid.
The photoconductors mentioned in the French Pat. specification are
advantageously partly or wholly substituted by the photoconductive
substances applied according to the present invention.
Suitable thermolysable binding agents belong to the class of the
polyacrylic acid esters and polymethacrylic acid esters, e.g.
polymethyl methacrylate, polyethyl methacrylate and polyethyl
acrylate.
The thickness of the photoconductive layers of the present
invention is not critical but is open to choice within a wide range
according to requirements in each individual case. Good results are
attained with photoconductive layers of a thickness between 1 and
30 .mu. preferably between 3 and 20 .mu. . Too thin layers do not
have a sufficient insulating power in the absence of active
electromagnetic radiation, whereas too thick layers require
extensive exposure times. The photoconductor may be used in a
self-supporting or supported layer.
In the manufacture of electrophotographic recording materials
according to the present invention preferably a relatively
conductive support for the recording layer is used, e.g. an
electroconductive sheet or plate, or an insulating sheet or plate
covered with an electro-conductive interlayer. By
electro-conductive plate or sheet is understood a plate or sheet
whose electrical resistivity is smaller than that of the
non-irradiated (dark-adapted) photoconductive layer, i.e., in
general smaller than 10.sup.9 ohm.cm and preferably is at least 100
times as small as that of the recording layer. Supports whose
resistivity is not higher than 10.sup.7 ohm.cm are preferred. The
recording layers themselves have preferably an electrical
insulating power as high as possible without affecting too much the
photosensitivity by means of too high an amount of insulating
binding agent. Preferably the recording layers have in
non-irradiated state (dark-adapted state) a resistivity of at least
10.sup.9 ohm.cm.
Suitable conductive plates are, e.g., plates of metals such as
aluminium, zinc, copper, tin, iron, or lead.
Suitable electro-conductive interlayers for insulating supports
are, e.g., vacuum-coated metal and conductive metal compound (metal
oxide or metal salt) layers such as silver, tin, aluminium,
titanium dioxide and copper iodide conductive layers, transparent
conductive polymer layers, e.g. applied from polymers containing
quaternized nitrogen atoms, such as those described in the United
Kingdom Pat. specification No. 950,960 filed Sept. 23, 1960 by
Gevaert Photo-Producten N.V., or layers containing conductive
particles, e.g. carbon black and metal particles dispersed in a
binder. The binder used for said particles has a resistivity
preferably lower than 10.sup.6 ohm.cm. A suitable binder for that
purpose is gelatin.
It is possible to produce transparent photoconductive recording
materials by applying the photoconductive compounds together with a
suitable binder (if necessary) from a clear solution to a
conductive transparent base or a transparent insulating base coated
with an electroconductive transparent interlayer.
As transparent bases resin sheets having an optical density of not
more than 0.10 are preferred, e.g., a sheet made of polyethylene
terephthalate or cellulose triacetate. The conductive interlayer
preferably consists of a metal coating, e.g. , a vacuum-coated
aluminium layer having an optical density of not more than 0.30, or
of a conductive transparent polymer layer composed, e.g., of an
organic polyionic polymer, e.g. a polymer containing quaternized
nitrogen atoms such as a quaternized polyethylene-imine.
In reproduction techniques wherein the prints are to be produced on
an opaque background preferably a paper sheet is used as support
for the recording layer.
Paper sheets that have an insufficient electrical conductivity are
coated or impregnated with substances enhancing their conductivity,
e.g. by means of a conductive overcoat such as a metal sheet
laminated thereto.
As substances suited for enhancing the conductivity of a paper
sheet and which can be applied in the paper mass are particularly
mentioned hygroscopic compounds and antistatic agents as described,
e.g., in the United Kingdom Pat. specification No. 964,877 filed
May 2, 1960 by Gevaert Photo-Producten N.V., and antistatic agents
of polyionic type, e.g. CALGON CONDUCTIVE POLYMER 261 (trade mark
of Calgon Corporation, Inc. Pittsburgh, Pa., U.S.A.) for a solution
containing 39.1 percent by weight of active conductive solids,
which contain a conductive polymer having recurring units of the
following type : ##SPC20##
Paper sheets are preferably impermeabilized to organic solvents,
e.g. by means of a water-soluble colloid or by strongly hydrating
the cellulose fibers such as in the case of glassine paper.
In order to prepare an electrophotographic material according to
the present invention various techniques may be applied.
In practice, the photoconductive substances involved, either alone
or together with other additives such as those described above,
preferably are first dissolved or dispersed in a suitable organic
solvent such as a chlorinated hydrocarbon, e.g. methylene chloride.
The solution or dispersion thus obtained is uniformly spread on a
surface of a suitable support, e.g. by centrifuging, spraying,
brushing, or coating. Thereupon the layer formed is dried in such a
way that a solid photoconductive layer is formed on the surface of
the support.
Recording materials according to the present invention can be used
in any of the different techniques known in recording with the aid
of photoconductors. According to a preferred embodiment they are
used in a technique based on the discharge of an electrostatically
charged recording layer by exposure to light.
Photoconductive recording materials prepared according to the
present invention can be used in exposure units equipped with
incandescent lamps, so that they need not be exposed with light
rays rich in ultraviolet such as those emitted by a high-pressure
mercury vapour bulb.
The electrostatic charging of photoconductive recording elements
according to the present invention can be effected according to any
method known in electrophotography, e.g. by friction with a smooth
material, with a material possessing a high electric resistance,
e.g. a cylinder coated with polystyrene, by corona discharge, by
contact charge, or by discharge of a capacitor.
Recording materials containing the said organic photoconductive
substances can be used in a recording technique comprising a
negative corona charging as well as in a recording technique
comprising a positive corona charging.
In order to obtain an electrostatic image it is possible to effect
the charging and exposure steps simultaneously and even to expose
the recording layer image-wise before charging since a conductivity
image is formed that is not destroyed immediately, especially if
diazonium salts are used in the recording element. It is preferred,
however, that the charging is effected before image-wise
exposure.
The electrostatic latent image can be converted into a visible
image either on the electrophotographic material wherein the latent
image was formed, or on a material to which the electrostatic
latent image was transferred, e.g. by application of the method
described in the Belgian Pat. specification No. 529,234 filed May
29, 1954 by Chester Floyd Carlson.
The conversion of the original or transferred latent image into a
visible image can occur according to one of the techniques known in
electrophotography, wherein use is made of a conductivity pattern
(e.g. electrolysis) or the electrostatic attraction or repulsion of
finely divided coloured substances, which, e.g., are present in a
powder mixture, in an electrically insulating liquid (e.g. in the
form of a suspension) or in a gas (e.g. in the form of an aerosol),
or wherein electrostatic attraction is used for selectively wetting
charged portions of the recording layer, as described in the United
Kingdom Pat. specification Nos. 1,020,505 filed Nov. 8, 1961 and
1,033,419 filed Nov. 26, 1962 both by Gevaert Photo-Producten
N.V.
When the sign of the charge of the developing powder or developing
liquid is properly chosen, either a negative or a positive print
can be obtained from any original. If both printing material and
developing powder or developing liquid have the same sign of
charge, the powder only adheres to the discharged areas so that a
negative print is obtained. If the signs of the recording material
and of the developing powder or developing liquid differ, a
positive print is obtained.
If a coloured powder is used for making visible the latent image,
the visible image obtained can, if necessary, be fixed according to
one of the methods known in electrophotography, e.g., by heating,
or it can be transferred to another support, e.g. according to the
method described in the United Kingdom Pat. specification No.
658,699 filed Apr. 14, 1949 by Battelle Memorial Institute and
fixed thereon.
The present heterocyclic organic photoconductive compounds can also
be supplied in a thermoplastic recording process to form a
ripple-image as described, e.g., in the United Kingdom Pat.
specification No. 964,881 filed May 17, 1960 by Gevaert
Photo-Producten N.V.
Evidently the present invention by no means is limited to one or
other particular embodiment of using the electrophotographic
material containing the photoconductive compounds as described
herein. The exposure technique, the charging method, the formation
of the charge pattern, the transfer of such pattern if applied, the
developing method, and the fixation or the transfer of the
developing material pattern may be modified or adapted.
The composition of the recording materials used in these methods
may be adapted to the requirements of the recording process
used.
Electrophotographic materials according to the present invention
can be employed in reproduction techniques, wherein different kinds
of electromagnetic radiations are used, e.g. visible light,
U.V.-radiation, X-rays and .gamma.-rays.
The following examples illustrate the present invention.
The percentages and ratios are by weight unless otherwise
indicated.
EXAMPLE 1
An aluminium-laminated paper sheet was coated with the following
composition:
10 % by weight solution in methylene chloride of an organic
photoconductor listed in Table I or II 50 ml. copoly(vinyl
chloride/vinyl acetate/maleic anhydride) (mol ratio 86.5/13.3/0.2)
5 g 1,2-dichloro-ethane 45 ml.
The coating was carried out in such a ratio that the dried
photoconductive layer contained 2 g of photoconductor per sq.m.
After a negative corona charging with a potential difference of
-6,000 V between the corona wires and the ground, the charged
recording layer was contact-exposed for 30 sec through a step wedge
having 0.20 log exposure increments. In this exposure 5 Osram
(trade name) L 20 fluorescent tubes, mainly emitting in the U.V.
range and the shorter wavelengths of the visible spectrum were
placed at a distance of 20 cm from the recording layer.
The latent wedge image obtained was electrophoretically developed
by means of an electrophoretic developer prepared by diluting the
concentrated developer composition described hereinafter in a
volume ratio of 15/1,000 by means of ISOPAR H (an isoparaffinic
hydrocarbon mixture having a boiling range of
177.degree.-188.degree. C sold by Esso Belgium N.V., Antwerp,
Belgium):
carbon black (average particle size: 20 nm) 30 g zinc monotridecyl
phosphate as dispersing agent 1.5 g ISOPAR H (trade name) 750 ml.
resin solution prepared as described hereinafter 150 g
The resin binder solution was prepared by heating 500 g of ALKYDAL
L 67 (of Farbenfabriken Bayer A.G., Leverkusen, W.Germany for a
linseed oil-modified (67 percent by weight) alkyd resin) and 500 ml
of white spirit containing 11 percent by weight of aromatic
compounds at 60.degree. C till a clear solution was obtained, and
subsequent cooling.
A black positive copy of the wedge original on a transparent base
was obtained.
From the wedge prints obtained the relative speed values of the
developed materials were calculated based on a comparison of the
number of non-toned (discharged) steps present in the wedge prints
obtained with material containing a photoconductor of Table I or II
with the number of non-toned steps produced in a material
containing photoconductor number 3 of Table II to which is given
arbitrarily the speed value 100.
Number of compound of Relative Speed values Table I or II 1,I 25
2,I 2.5 1,II 250 2,II 250 3,II 100 5,II 160 6,II 160 7,II 60
EXAMPLE 2
An electrophotographic recording material was prepared by coating
onto an aluminium laminated paper a solution containing:
10% by weight solution in methylene chloride of an organic
photoconductor listed in Table I or II 50 ml. copoly(vinyl
chloride/vinyl acetate/maleic anhydride) (mol ratio 86.5/13.3/0.2)
5 g Rhodamine B (C.I. Basic Violet 10 C.I. 45,170) 0.025 g
1,2-dichloroethane 45 ml.
The dried recording layer contained 2 g of photoconductor per
sq.m.
The coated samples were negatively charged with a negative corona
having a potential difference of -6,000 V between the corona wires
and the ground.
The charged recording layer was contact-exposed for 6 sec. through
a step-wedge having 0.20 log exposure increments. In the exposure
tungsten filament lamp light was used.
The latent wedge images were electrophoretically developed as
described in Example 1.
The relative speed values of the developed materials were compared
with the electrophotographic material containing photoconductor
number 3 of Table II which is given arbitrarily the speed value
100.
Number of compound of Relative Speed values Table I or II 1,I 25
2,I 1 3,I 25 4,I 1 6,I 2.5 1,II 100 2,II 40 3,II 100 5,II 250 6,II
100 7,II 40
EXAMPLE 3
To a polyethylene terephthalate support of 100 .mu. a conductive
transparent coating was applied from an aqueous solution of gelatin
and CALGON CONDUCTIVE POLYMER 261 in a weight ratio of 2:1. Coating
was carried out in such a way that the dried coating contained 2 g
of gelatin per sq.m. The electric resistivity of the coating was 1
.times. 10.sup.6 ohm per sq.cm.
An electrophotographic recording material was prepared by coating
onto said conductive layer a solution consisting of
methylene chloride 45 ml. 1,2-dichloro-ethane 45 ml. ##SPC21## 5 g
copoly (vinyl chloride/vinyl acetate/maleic anhydride)(molar ratio
86.5/13.3/0.2) 5 g Rhodamine B (C.I. Basic Violet 10; C.I. 45,170)
0.025 g
The dried recording layer containing approximately 3 g of
photoconductor per sq.m., was charged with a negative corona and
contact-exposed with 100 lux.sec with the same light source as in
Example 2. The latent image was electrophoretically developed for 5
sec. with the developer described in Example 1. A good copy of the
original was obtained.
EXAMPLE 4
To a polyethylene terephthalate support of 63 .mu. a conductive
transparent coating was applied from
a 10 % aqueous solution of polystyrene sulphonic acid sodium salt
40 ml. methanol 60 ml.
The coating was carried out in such a way that the dried material
contained 1.75 g of polystyrene sulphonic acid sodium salt per
sq.m. The electrical resistivity was 5 .times. 10.sup.6 /cm2.
An electrophotographic recording material was prepared by coating
onto said conductive layer at a coverage of 3 g per sq.m of
photoconductor a solution containing : ##SPC22## 5 g copoly(vinyl
chloride/vinyl acetate/maleic anhydride)(molar ratio 86.5/13.3/0.2)
5 g methylene chloride 45 g 1,2-dichloroethane 45 g
After a negative corona charging with a potential difference of
-6,000 V, the charged recording layer was contact-exposed for 30
sec through a positive transparency of a test chart with 5 Osram
(trade name) L 20 fluorescent tubes at a distance of 20 cm from the
recording layer.
After the exposure the latent image was developed for 5 sec with a
triboelectrically charged positive toner on the base of three parts
by weight of pitch, four parts by weight of colophony and three
parts by weight of carbon black.
A contrasty transparent positive copy of the transparency was
obtained.
EXAMPLE 5
The effect on the speed of electrophotographic recording materials
resulting from a few chemical sensitizers was examined.
Therefor the following photoconductive compositions were coated on
an aluminium laminated paper:
10 % by weight solution in methylene chloride of the organic
photoconductor number 2 of Table II 50 ml. copoly(vinyl
chloride/vinyl acetate/maleic anhydride)(molar ratio 86.5/13.3/0.2)
5 g a chemical sensitizer listed in Table IV 0.05 g.
The dried layers contained 2 g of photoconductor per sq.m.
Processing of the materials was carried out in the same way as
described in Example 1. The relative speed values are listed
hereinafter. ##SPC23## ##SPC24##
EXAMPLE 6
Electrophotographic recording materials were prepared by coating
onto a conductive layer as described in Example 3 a composition
containing :
compound number 4 of Table II 5 g copoly(vinyl chloride/vinyl
acetate/maleic anhydride)(molar ratio 86.5/13.3/0.2) 5g methylene
chloride 45 ml 1,2-dichloroethane 45 ml a sensitizing dye as listed
in the table V 0.025 g
The recording layers were charged, exposed and developed as
described in Example 3.
From the obtained prints the relative speed values were calculated
based on a comparison of the spectrally sensitized materials with
the material without spectral sensitizer to which arbitrarily the
speed value of 100 was given.
The relative speed values are listed hereinafter. ##SPC25##
##SPC26## ##SPC27##
EXAMPLE 7
An electrophotographic recording material was prepared by coating
onto a conductive layer as described in Example 3 a solution
containing : ##SPC28## ##SPC29##
The coating was carried out at a coverage of 1.35 g of
photoconductor per sq.m.
After a negative corona charging the recording layer was exposed in
a microfilm camera for 10 sec. with 1,500 lux to a halftone
multicolour original. The diaphragma setting was 4.5 and the
original was reduced optically 20 times. The obtained electrostatic
charge image was developed as described in Example 1.
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