CA1139599A - Imaging member including a n,n'substituted ¬1,1'-biphenyl|-4,4'-diamine charge transport material and a bis-or tris- (disubstituted amino phenyl) methane stabilizing compound - Google Patents

Abstract

Abstract of the Disclosure An imaging member comprising a hole generation layer and a contiguous hole transport layer, said hole transport layer comprising a transparent electrically inactive polycarbonate resinous material having a residual amount of a halogen containing organic solvent therein and dispersed therein from about 25 to about 75 percent by weight based on said transport layer composition of a diamine, said charge transport layer being substantial-ly nonabsorbing in the spectral region at which the hole generation layer generates and injects photogenerated holes, but being capable of supporting the injection of photogenerated holes from said photoconductive material and transporting said hole through said charge transport layer, said charge transport layer also containing a stabilizing proportion of a di or triaryl methane compound of the general formula:

Description

IMAGING SYSTEM
Back~round of the Invention This invention relates in general to xerography and more specifi-cally to a novel photosensitive device.
In recent years, interest has been shown in flexible electrophoto-graphic plates for use in high speed office copying machines. Some of these plates are multilayered devices comprising, a conductive substrate layer, an adhesive-blocking interface layer, a charge generation layer and a charge transport layer. The charge transport layer comprises an organic charge transport molecule dissolved in a polymeric matrix material. This layer is substantially nonabsorbing in the spectral region of intended use, i.e. visible light, but is "active" in that it allows (1) injection of photogenerated holes from the charge generation layer and (2) efficient transport of these charges to the surface of the transport layer to discharge a surface charge thereon.
One class of hole transport molecules, N,N'-diphenyl-N,N'-bis-(alkylphenyl~[l,lt-biphenyl~-4,4'-diamines, has been extensively studied as solutions or dispersions in polycarbonate polymers. The conductivity of this class of compounds in polycarbonate polymers has been found to increase under certain circumstances. When photoreceptor devices employing this class of compounds have a residual amount of a halogen-containing alkane solvent in the transport layer and they are subjected to ~traviolet radiation, a condition known as "cycle downl' progressively develops as the device is cycled 'in the xerographic process. "Cycle down" refers to the progres~ive increase in conductivity of the transport layer and in a relatively short periodof time the charge acceptance of the device deteriorates. Also, special precautions hqve to be taken with regard to the handling of the devices employing these compounds. They cannot be stored or left exposed to ambient room light for any length of time because fluorescent lamps employed in most buildings contain a UV component. This U~ radiation causes devices left exposed to the room light to undergo gradual deterioration resulting in an increase in the conductivity of the transport layer.

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-la-Objects of the Invention It is therefore an object of an aspect of this invention to provide a novel photosensitive device less susceptible to the deleterious effects o ultraviolet radiation degradation in the transport la~er thereof.
It is an object of an aspect of this invention to provide an electrophoto-r-3~

graphic device free of "cycle down" problems caused by ultraviolet light induced increased conductivity.
Prior Art Statement Chemical stabilization of the physical properties of polymers has been well pursued and a host of additives are available which stabilize various polymers against ultraviolet induced discoloration or ultraviolet induced mechanical failures. As far as is known, however, no study has been done to date on the chemical stabilization of electronic properties. By electronic stabilization is meant the eliminating or minimizing of ultraviolet radiation-10 induced traps or ultraviolet radiation-induced dark decay and the like. To beuseful as an electronic stabilizer in a cyclic duplicating machine, the additive, in addition to preventing ultraviolet degradation, has to meet another stringent requirement. The additive should not introduce traps of its own under cyclic conditions, since even a small number of traps resuIt in the 15 cumulative trapping phenomenon generally referred to as "cycle up". The trap could be an isolated electronic state of the additive or it could resuit from the additive changing the character of the dispersion of the host molecule in the binder matrix. As indicated, no prior art appears to have dealt precisely with the problem outlined above.
Summary of the Invention The foregoing objects and others are accomplished in accordance with this invention by providing a photosensitive member comprising a generator layer and an improved transport layer. The transport layer comprises a solution or dispersion of a diamine of the class defined below, in 25 a polycarbonate resin which also contains a residual amount of a halogen-containing organic solvent and a stabilizing proportion of a diaryl or triaryl methane compound of the class defined below.
It has been found that the addition to the transport layer of a diaryl or triaryl methane compound significantly reduces or eliminates photo-30 reactions leading to the deleterious effects of ultraviolet radiationknown as"cycIe down". The use of this class of additives has no apparent deleterious effects of its own on the chemical or electrical properties of the hole transport layer. This is indeed unexpected because this class of compounds, i.e. the diaryl or triaryl methane compounds are known in and of themselves 35 as effective charge transport compounds when dissdved in a polycarbonate.
However, these compounds when used as the charge transport molecule, are L, .~ c_ photooxidatively unstableO As photoreceptor devices employ-ing this class of compounds are subjected to ultraviolet radiation, a condition known as "cycle up" progressively devel~ps as the device is cycled in a xerographic machine.
"Cycle up" refers to the bulk trapping of holes in the transport layer and in a relatively short period of time, efficient discharge of the charged surface of the photo-receptor is lost.
Therefore, it is indeed unexpected that a compound which, when used alone as a charge transport material, is susceptible to the deleterious effects of UV light, would effectively inhibit the deleterious effects o~ UV
light in a different compound.
An aspect of the invention is as follows:
]5 In an imaging member comprising a hole generation layer and a contiguous hole transport layer, said generation layer comprising a photoconductive material exhibiting the capability of photogeneration of holes and injection of said holes, said hole transport layer comprising a transparent electrically inactive polycarbonate resinous material having a residual amount of a halogen-containin~
organic solvent therein, and dispersed therein from about 25 to about 75 percent by weight based on said transport layer composi~ion of a charge transport compound within the scope of the following structural furmula:
~\ .~
N - CO~N

wherein Ris ~ - CH2 . \
,....~, 3 5r~
-3a-and wherein X is independently selected from the group consisting of an alkyl group having from 1 to about 4 carbon atoms and chlorine in the ortho, meta or para position, said charge transport layer being sub-stantially nonabsorbing in the spectraI region at whichthe photoconductive material generates and injects photo-generated holes but being capable of supporting the injection of photogenerated holes from said photocond-uctive material and transporting said holes through said charge transport layer, the improvement consisting of the inclusion in said transport layer of a stabilizing compound within the scope of the following structural formula:

~ /
N

~ ~'\
~ ~ 20 R3 .
R4 ~ ~ ~ R3 ~:

, N
: ~ 3 0 / \
Rl R~
~;~ wherein Rl and R2 are independently selected from the group consisting of a Cl-C8 alkyl, aryl, alkaryl and aralkyl, where said aryl is a phenyl group or a con-: densed ring group, where the alkyl group of said alkaryl :

:

-3b-and aralkyl is a Cl-C4 group, R3 is independently selected from the group consisting of hydrogen and CH3; and R4 is the same as Rl and R2 or a cLisubstituted aminophenyl group wherein the substituents are independently selected from the group consisting of a Cl-C8 alkyl, aryl, alkaryl and aralkyl as defined supra, said stabiliziny compound being present in an amount sufficient to at least minimize the deleterious effects of ultraviolet radiation.
In general, the advantages of the invention will become apparent upon consideration of the ~ollowing disclosure of the invention, especially when ta~en in conjunction with the accompanying drawing wherein:
Brief Description of the Drawlng The Figure is a schematic illustration of one of the members of the instant invention which comprise a photoreceptor having a charge generation layer overcoated with a charge transport layer.
Detailed Description of the Drawing and Invention ~e~erring to the Figure, reference character 30 designates an imaging member which comprises a supporting substrate 11 having a charge generator layer 12 thereon.
Substrate 11 is preferably comprised of any suitable con-ductive material. Typical conductors comprise aluminum, steel, nickel, brass or the like. The substrate may be rigid or flexible and of any convenient thickness. Typical substrates include flexible belts of sleeves, sheets, webs, plates, cylinders and drums. The substrate or support may also comprise a composite structure such as a thin conductive coating contained on a paper base; a plastic coated with a thin conductive layer such as aluminum, nickel or copper iodide; or glass coated with a thin con-ductive coating of chromium or tin oxide.

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--3c--In addition, if desired, an electrically insulating substrate may be used. In this case, an electric charge, equivalent to a conductive layer, may be placed upon the insulating member by double corona charging techniques well known or disclosed in the art. Other modifications using an insulating 5 substrate or no substrate at all include placing the imaging member on a conductive backing member or plate and charging the surface while in contact with said backing member. Subsequent to imaging, the imaging member may then be stripped from the conductive backing.
Generator layer 12 contains photoconductive particles dispersed randomly without orientation in binder 14.
Binder material 14 may comprise any electrically insulating resin such as those disclosed in Middleton et al U.S. Patent 3,121,006. Specific examples are polystyrene, acrylic and methacrylic ester polymers, polyvinylchlorides, etc. When using an electrically inactive or insulating resin/ it is essential that there be particle to particle contact between the photoconductive particles. This necessitates that the photoconductive material be present in an amount of at least about 10% by volume of the binder layer with no limit on the maximum amount of photoconductor in the binder layer. If the matrix or binder comprises an active material, e.g., polyvinyl carbazole, the photoconductive material need only comprise about 1% or less by volume of the binder layer with no limitation on the maximum amount of photoconductor in the binder layer.
The thickness of binder layer 12 is not critical. Layer thicknesses from about 0.05 to ~0.0 microns have been found to be satisfactory.
The photoconductive particles 13 may be any material capable of photogenerating holes and injecting photogenerated holes into the contiguous charge transport layer 15. Any suitable inorganic or organic photoconductor and mixtures thereof may be employed.
Inorganic materials include inorganic crystalline photoconductive compounds and inorganic photoconductive glasses. Typical inorganic compounds include cadmium sulfoselenide, cadmium selenide, cadmium sulfide and mixtures thereof. Typical inorganic photoconductive glasses include amorphous selenium and selenium alloys such as selenium-tellurium, selenium-tellurium-arsenic and selenium-arsenic and mixtures thereof. Selenium may ~4~
a also be used in a crystalline form known as trigonal selenium.
Typical organic photoconductive materials which may be used as charge generators include phthalocyanine pigment such as the X-form of metal free phthalocyanine described in U.S. Patent 3,357,989 to Byrne et al; metal phthalocyanines such as copper phthalocyanine;
quinacridones available from duPont under the tradename Monastral Red, Monastral Violet and Monastral Red Y;
substituted 2,4-diamino-triazines disclosed by Weinberger in U.S. Patent 3,445,227; triphenodioxazines disclosed by Weinberger in U.S.

r;~q~l Patent 3,442,781; polynuclear aromatic quinones available from Allied Chemical Corporation under the tradename Indo I)ouble Scarlet, Indofast Violet Lake B, Indofast Brilliant Scarlet and Indofast Orange. The photo-conductive particles may be present in the generator layer in from 0.5% to 5 about 95% by volume depending on the character of the binder material.
It is to be understood that the generator layer need not be dispersed photoconductive particles in a resin binder but can be Q homogene-ous layer, such as, amorphous selenium, selenium alloys e.g. selenium-tellurium-arsenic alloys and, in fact, any other charge generating photocon-10 ductive material which can withstand a minimum flexing stress required in aflexible photoreceptor.
Active layer 15 comprises a transparent electrically inactive polycarbonate resinous material having dispersed therein from about 25 to 75~6 by weight of the composition of one or more of the diamines within the 15 scope of the following structural formula:
~\ i~

2 0 N ~ N

R R

wherein R is @5~ or ---CH

and wherein X is independently selected from the group consisting of an alkyl group having from 1 to about 4 carbon atoms (e.g. rnethyl, ethyl, propyl, butyl, etc.) and chlorine in the ortho, meta or para position.
In general, the thickness of active layer 15 would be from about 5 to 100 microns, but thicknesses outside this range can also be used.
The preferred polycarbonate resins for the transport layer have a molecular weight from about 20,000 to about 120,000, more preferably from about 50,000 to about 120,000.

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Materials most preferred as the electrically inactlve resinous material are poly(4,4'-isopropylidene-diphenylene carbonate) having molecular weights of from about 25,000 to about 40,000, available as Lexan~ 5, from about 40,000 to about 45,ûO0, available as Lexan(~ 1~1, both from the ~;eneral Electric Company; and from about 50,000 to about 120,000 available as Mak-rolon~, from Farbenfabricken Bayer AG; and from about 20,000 to about 50,000 available as Merlon~), from Mobay Chemical Company.
Active layer lS, as described above, is substantially nonabsorbing to light in the wavelength region employed to generate holes in the photo-10 conductive layer. This preferred range for xerographic utility is from about 4,000 to about 8,000 angstrom units. In addition, the photoconductor should be responsive to all wavelengths from 4,000 to 8,000 angstrom units if pan-chromatic responses are required. All photoconductor-active material com-binations of the instant invention result in the injection and subsequent trans-15 port of holes across the physical interface between the photoconductor and the active material.
In order to effectively dissolve the charge transport diamine compound in the polycarbonate matrix, a suitable mutual solvent system must be employed. Methylene chloride, i.e. CH2C12, is effective for this purpose, 20 although other solvents such as chloroform and 1,2-dichloroethane can be employed. Non-halogen-containing organic solvents such as tetrahydrofuran are found to be poor solvents for the high molecular weight polycarbonate.
Dispersed or dissolved in the transport layer in order to greatly minimize or eliminate the deleterious effects of ultraviolet radiation is a 25 stabilizing proportion of one or more of the di or triphenylmethanes within the scope of the following structural formula:

l~

1~

~ ~ R3 Rd~ C - -~ R3 (~ ~/ R3 N

R/ \R

wherein Rl and R2 are independen~y selected from the group consisting of a Cl-C8 alkyl, aryl, alkaryl and aralkyl~ where said aryl is a phenyl group or a condensed ring group, where the alkyl group of said alkaryl and aralkyl is a Cl-C4 group, R3 is independently selected from the group 25 consisting of hydrogen and CH3; and R4 is the same as Rl and R2 or a di-substituted aminophenyl group wherein the substituents are independently selected from the group consisting of a Cl-C8 alkyl, aryl, alkaryl and ar&lkyl as defined supra.
Examples of compounds of this class are as follows: bisl4,N,N1-30 diethylamin~2-methylphenyl) phenyl methane; 1-bis-(4-dimethylamin~
phenyl~l-phenyl ethane; and bis-[4-bis-(phenylmethyl) amin~2-chlorophenyl]
phenyl methaneO
This compound may be employed in any amount whieh will inhibit or greatly minimize the deleterious effects of UV light on the charge 35 transport diamine compound. Generally, it is preferred that the inhibiting compound be present in a weight ratio of from 0.0005:1 to 0.1:1.

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The following examples further specifically define the present invention with respect to preparing the photosensitive members. The percentages are by weight unless otherwise indicated. The examples are intended to illustrate various comparisons and preferred embodiments of the 5 instant invention.
EXAMPLE I
A generator layer is prepared as follows; 2.~ ~rams of poly(N-vinylcarbazole) is dissolved in 42 mls of a 1:1 mixture of tetrahydrofuran and toluene. To this is added 2.4 grams of chemically precipitated trigonal 10 selenium and the mixture is then ball milled for about 72 hours in a 4 ounce bottle employing 300 grams of 1/8 inch diameter stainless steel shot. An approximately 2 micron thick layer is applied from a coating of this slurry onto a substrate of aluminized Mylar which had been previously coa~ed with a thin adhesive film, such as, duPont 4900~) polyester. This layer is heated at 15 100 C for 18 hours in vacuum.
An approximately 25 micron thick transport layer is formed on top of the generator layer as follows:
1 gram of Makrolon~3) polycarbonate and 1 gram of N,N~diphenyl-N,N~bis(3-methylphenyl~[l,l~-biphenyl] -4,4'-diamine are dissolved in 10 mls of 20 methylene chloride. A layer of 25 microns thick is overcoated onto the generator layer and heated at 80 C in vacuum for 72 hours so as to reduce the amount of residual methylene chloride to a trace, i.e. less than 0.01 weight percent in the transport layer.
The xerographic testing of this device" as well as the devices 25 described in subsequent examples, is carried out as follows: the layered device is negatively charged to a potential of about 1200 volts and the dark decay monitored for 5 seconds. The device is then exposed to a 2 microsecond flash of 4330 Angstrom units wavelength and about 15 Ergs/em2 intensity. The device of this example is completely discharged by the light 30 source, indicating that it is a xerographically operable device.
To examine the ultraviolet light stability of the device, it is exposed to an intense long wave UV source for 2 minutes, total photons 6 X
1016tcm2, and retested xerographically as above. The dark decay of the device is virtually the same as the rate of decay of the device before 35 exposure to UV light. This shows that the performance of the device is substantially unaffected by ultraviolet light.

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EXAMPLE II
This device is fabricated of the same materials and in the same manner as Example I except that the device is heated at 80C in vacuum for only 2 hours, instead of 72 hours, with the result that about 0.1 weight percent5 methylene chloride remains in the transport layer. The device is xerographi-cally tested before and after subjecting the device to ultraviolet light as in Example I. As a result vf the UV exposure, the dark decay increased significantly and could not be tolerated in a practical device.
EXAMPI E III
This device is fabricated as in Example II except that the solvent employed to coat the transport layer is tetrahydrofuran instead of methylene chloride. One gram of MakrolonB)polycarbonate and 1 gram of N,N'-diphenyl-N,N'-bis(3-methylphenyl~[l,l'-biphenyl]-4,4'-diamine are dissolved in 10 mls of tetrahydrofuran. The polycarbonate is only partially soluble in the tetra-15 hydrofuran and difficulty was experienced in filtering the w~dissolved fraction from the system. The undissolved fraction must be removed otherwise efficient charge transport is sacrificed. After removal and deposition of the transport layer on the generator layer, the device is heated at 80 C for about 2 hours. This leaves a residual of about 0.1 percent by weight tetrahydrofuran 2 0 in the transport layer.
The device is xerographically tested before and after the same degree of UV exposure as above. No increase in dark decay is observed as a result of the IJV energy. This indicates that no increase in dark decay or degradation of the device is caused by the presence of a residual of tetra-5 hydrofuran and the inîluence of ultraviolet radiation.EXAMPLE IV
A device is prepared having the generator layer of Example 1. A
transport layer is formed on top of this generator layer as follows: a solution of 1 gram of Makrolon~ polycarbonate and 1 gram of bis(4,N,N'-diethylamino-30 2-methylphenyl) phenyl methane in 10 mls of methylene chloride. A layer of approximately 25 microns is deposited on the surface of the generator layer and heating the device at 80 C for about 2 hours in vacuum.
When xerographically tested before and after subjecting it to the same degree of UV exposure as in Example I, no increase in dark decay is 35 observed. However, the degradation of the transport layer appears as a tremendous increase in residuals when xerographically tested after exposure .3r~d~

to UV radiation. The residual is the potential measured after the negatively charged device is exposed to the 4330 Angstrom units wavelength flash source. The residual potential occurs from charge trapping in the transport layer.
EXAMPLE V
This device is the same as that in Example IV except that tetra-hydrofuran is the solvent employed to coat the transport layer. Thus, the transport layer is coated from a solution of 1 gram of Makrolon~
polycarbonate and 1 gram of bis(4-N,N'diethylamino-2-methylphenyl) phenyl 10 methane in 10 mls of tetrahydrofuran. Undissolved polycarbonate is filtered from the solution. After removal and deposition of the transport layer on the generator layer the device is heated at 80C for 2 hours in vacuum. The transport layer is approximately 25 microns thick.
When xerographlcally tested before and after subjecting the 15 device to UV exposure9 a tremendous increase in residual potential is observed.
The conclusions from the results of Examples I-V are as follows:
when the diamine molecule identified in Example I is dissolved in a polycarbonate which contains a significant residual amount of methylene 20 chloride solvent and this system is exposed to UV radiation the de~adation appears as an increase in conductivity and when the trisubstituted methane molecule identified in Example IV is dissolved in polycarbonate and exposed to UV radiation, the degradation appears as charge carrier trapping, resulting in an increase in residual potenffal.
EXAMPLE VI
The generator layer of Example I is prepared. A transport layer as prepared from a solution of 1 gram of Makrolon~ polycarbonate, 0.995 gram of N,N'-diphenyl-N,N'-bis(3-methylphenyl~[l,l'-biphenyl]-4,4'-diamine and 0.005 gram of bis(4'-N,N~diethylamino-2-methylphenyl) phenyl methane in 10 30 mls of methylene chloride. A layer of this combination is deposited onto the generator layer so that after removal of the methylene chloride solvent an approximately 25 micron layer remains. The device is heated at 80C for about 2 hours in vacuum. This reduces the methylene chloride content to about 0.1 weight percent.
When xerographically tested before and after subjecting it to UV
exposure, there was no increase in dark decay. Also, there was no increase in the residual patentials. The degradation of the diamine containing layer is prevented by the addition of the substituted methane molecule.
EXAMPLE VII
This device is similar to the device of Example VI except that the 5 transport layer composition is varied slightly. The transport layer is coated from a solution of 1 gram of Makrolona~ polycarbonate, 0.95 gram o the diamine and 0.05 gram of the substituted methane compound in 10 mls of methylene chloride. After deposition of the transport layer, the device is heated at 80 C for 2 hours in vacuum.
When xerographi--ally tested before and after being subjected to the UV exposure, no change in dark decay is observed. Further, no increase in residual potential is observed. The photodischarge of the device containing the diamine and the substituted methane compound in the polycarbonate is the same as that of the device containing no substituted methane, i.e.
15 Example II. These results prove that the UV degradation of the diamine in polycarbonate layers containing residual methylene chloride is prevented by the presence of the substituted methane compound. The presence of the methane compound does not adversely impact the charge transport character-istics of the transport layer.

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Claims (5)

WHAT IS CLAIMED IS:

1. In an imaging member comprising a hole generation layer and a contiguous hole transport layer, said generation layer comprising a photocon-ductive material exhibiting the capability of photogeneration of holes and injection of said holes, said hole transport layer comprising a transparent electrically inactive polycarbonate resinous material having a residual amount of a halogen-containing organic solvent therein, and dispersed therein from about 25 to about 75 percent by weight based on said transport layer composition of a charge transport compound within the scope of the following structural formula:

wherein R is or and wherein X is independently selected from the group consisting of an alkyl group having from 1 to about 4 carbon atoms and chlorine in the ortho, meta or para position, said charge transport layer being substantially nonabsorbing in the spectral region at which the photoconductive material generates and injects photogenerated holes but being capable of supporting the injection of photogenerated holes from said photoconductive material and transporting said holes through said charge transport layer, the improvement consisting of the inclusion in said transport layer of a stabilizing compound within the scope of the following structural formula:

wherein R1 and R2 are independently selected from the group consisting of a C1-C8 alkyl, aryl, alkaryl and aralkyl, where said aryl is a phenyl group or a condensed ring group, where the alkyl group of said alkaryl and aralkyl is a C1-C4 group, R3 is independently selected from the group consisting of hydrogen and CH3; and R4 is the same as R1 and R2 or a di-substituted aminophenyl group wherein the substituents are independently selected from the group consisting of a C1-C8 alkyl, aryl, alkaryl and aralkyl as defined supra, said stabilizing compound being present in an amount sufficient to at least minimize the deleterious effects of ultraviolet radiation.

2. The member of Claim 1 wherein the weight ratio of said stabilizing compound to said charge transport compound is from 0.0005:1 to 0.1:1.

3. The member of Claim 2 wherein said stabilizing compound is selected from the group consisting of bis(4'-N,N'-diethylamino-2-methyl-phenyl) phenyl methane; 1-bis-(4-dimethylaminophenyl)-1-phenyl ethane; and bis-[4-bis-(phenylmethyl) amino-2-chlorophenyl] phenyl methane.

4. The member of Claim 3 wherein said polycarbonate is poly(4,-4'-isopropylidene-diphenylene carbonate) having a molecular weight of from 20,000 to about 120,000.

5. The member of Claim 4 wherein said charge transport compound is N,N'-diphenyl-N,N'-bis(3-methylphenyl-[1,1'-biphenyl]-4,4'-di-amine.