[0001] This invention relates generally to photoreceptors and the preparation thereof, and
more particularly to photoreceptor substrates and their preparation.
[0002] In the process of fabricating photoreceptor substrates, there may result substrates
having surface blemishes, substandard dimensions, or both. Substrates having surface
blemishes and substandard dimensions are typically deemed unsuitable for use in photoreceptor
applications and are discarded since these substrates fail to meet testing requirements,
performance requirements, and/or customer perceptions. It would be economical if these
substandard substrates could be reclaimed for use as photoreceptor substrates.
[0003] In addition, there is a need for a photoreceptor substrate that suppresses optical
interference occurring within a photosensitive member. When not suppressed, the optical
interference results in a defect that resembles the grain in a sheet of plywood in
output prints derived from the exposed photosensitive member when the exposure is
a uniform, intermediate-density gray. There are numerous applications in the electrophotographic
art wherein a coherent beam of radiation, typically from a helium-neon or diode laser
is modulated by an input image data signal and is directed (scanned) across the surface
of a photosensitive medium which, in the case of "layered photoreceptors", has at
least a partially transparent photosensitive layer overlying a conductive ground plane
(also referred to as a substrate). A problem inherent in using these layered photoreceptors,
depending upon the physical characteristics, is the creation of two dominant reflections
of the incident coherent light on the surface of the photoreceptor, e.g., a first
reflection from the top surface and a second reflection from the top surface of the
relatively opaque conductive ground plane. This condition is shown in Fig. 1 where
coherent beams 1 and 2 are incident on a layered photoreceptor 6 comprising a charge
transport layer 7, charge generator layer 8, and a ground plane 9. The two dominant
reflections are from the top surface of layer 7, and from the top surface of ground
plane 9. Depending on the optical path difference as determined by the thickness and
index of refraction of layer 7, beams 1 and 2 can interfere constructively or destructively
when they combine to form beam 3. When the additional optical path traveled by beam
1 (dashed rays) is an integer multiple of the wavelength of the light, constructive
interference occurs, more light is reflected from the top of charge transport layer
7 and, hence, less light is absorbed by charge generator layer 8. Conversely, a path
difference producing destructive interference means less light is lost out of the
layer and more absorption occurs within the charge generator layer 8. The difference
in absorption in the charge generator layer 8, typically due to layer thickness variations
within the charge transport layer 7, is equivalent to a spatial variation in exposure
on the surface. This spatial exposure variation present in the image formed on the
photoreceptor becomes manifest in the output copy derived from the exposed photoreceptor.
Figure 2 shows the areas of spatial exposure variation (at 25x) within a photoreceptor
of the type shown in Figure 1 when illuminated by a He-Ne laser with an output wavelength
of 633 nm. The pattern of light and dark interference fringes look like the grains
on a sheet of plywood. Hence the term "plywood effect" is generically applied to this
problem.
[0004] US-A-4,067,782 discloses a process for nickel plating a cylindrically shaped hollow
core mandrel suitable for chromium plating for use in an electroforming process for
the production of endless seamless nickel xerographic belts.
[0005] US-A-5,069,758 discloses a process for suppressing the plywood effect in photoreceptors
by forming the ground plane surface with a rough surface morphology using an electroforming
process which leaves the surface with a matte-like finish.
[0006] US-A-5,096,792 discloses a layered photosensitive imaging member modified to reduce
the plywood effect. The modification described is to form the ground plane surface
with a rough surface morphology by various selective metal deposition methods.
[0007] It is an object of the present invention in embodiments to reclaim substandard photoreceptor
substrates.
[0008] It is a further object to provide a process for metal coating photoreceptor or imaging
member substrates.
[0009] It is still another object in embodiments to provide substrates with a metal layer
having a surface morphology effective for reducing or suppressing the plywood effect.
[0010] It is an additional object in embodiments to provide a layer of metal sufficient
to increase the dimensions of the substrate to the desired standard.
[0011] It is also an object in embodiments to metal coat photoreceptor substrates using
electroplating or electroless metal deposition techniques.
[0012] The present invention provides a process for the preparation of a photosensitive
imaging member comprising: (a) providing a photoreceptor substrate wherein the substrate
surface is marred by at least one surface blemish; (b) removing at least a portion
of the surface blemish when the blemish is a surface height defect, and optionally
removing at least a portion of the surface blemish when the blemish is a non-surface
height defect; and (c) depositing a layer of metal on the substrate, wherein the metal
layer has a surface appearance which conceals at least a portion of the underlying
substrate surface blemish remaining after step (b).
[0013] The invention further provides a process for the preparation of a photosensitive
imaging member according to claim 9 or 10 of the appended claims.
[0014] Preferably, the metal layer has a surface roughness sufficient to substantially suppress
the formation of a pattern of light and dark interference fringes upon exposure of
the photosensitive imaging member Preferably, the metal layer has a surface roughness
defined by one or more of the following parameters: R
a having a value ranging from about 0.05 to about 0.7 µm; R
q having a value ranging from about 1 to about 6 µm; R
t having a value ranging from about 0.5 to about 6 µm; R
pm having a value ranging from about 0.2 to about 2 µm; W
t having a value ranging from about 0.1 to about 1 µm; P
t having a value ranging from about 0.8 to about 6 µm. Preferably, the metal is copper
or nickel. Preferably, the metal layer is deposited by electroplating.
[0015] The phrase "surface blemish" or surface blemishes" refers to surface defects including
scrapes, nicks, scratches, coating defects, imperfections in the material of the substrate,
surface spots, discolorations caused by for example water spots, mixtures thereof,
and the like. A blemish may be generally a surface height defect such as scrapes,
nicks, scratches, bumps, and the like, or a non-surface height defect such as surface
spots, discolorations, and the like.
[0016] Other aspects of the present invention will become apparent as the following description
proceeds and upon reference to the Figures, in which:
[0017] Fig. 1 shows coherent light incident upon a prior art layered photosensitive medium
leading to reflections internal to the medium.
[0018] Fig. 2 shows a spatial exposure variation plywood pattern in the exposed photosensitive
medium of Fig. 1 produced when the spatial variation in the absorption within the
photosensitive member occurs due to an interference effect.
[0019] To prepare the metal coated photoreceptor substrate, there is first provided a formed
photoreceptor substrate. The term "formed" refers for example to a fabricated substrate
as distinguished from a substrate which is undergoing fabrication whether by electroforming,
by extrusion, or by any other conventional fabrication technique. The term "formed"
includes substrates having finished surfaces, such as by machining and/or buffing,
and unfinished surfaces. The substrate can be formulated entirely of an electrically
conductive material, or it can be an insulating material having an electrically conductive
surface. The substrate can be opaque or substantially transparent and can comprise
numerous suitable materials having the desired mechanical properties. The entire substrate
can comprise the same material as that in the electrically conductive surface or the
electrically conductive surface can merely be a coating on the substrate. Any suitable
electrically conductive material can be employed. Typical electrically conductive
materials include metals like copper, brass, nickel, zinc, chromium, stainless steel;
and conductive plastics and rubbers, aluminum, semitransparent aluminum, steel, cadmium,
titanium, silver, gold, paper rendered conductive by the inclusion of a suitable material
therein or through conditioning in a humid atmosphere to ensure the presence of sufficient
water content to render the material conductive, indium, tin, metal oxides, including
tin oxide and indium tin oxide, and the like. The substrate layer can vary in thickness
over substantially wide ranges depending on the desired use of the electrophotoconductive
member. Generally, the conductive layer ranges in thickness of from about 50Å to 10cm,
although the thickness can be outside of this range. When a flexible electrophotographic
imaging member is desired, the substrate thickness typically is from about 100Å to
about 0.015 mm. The substrate can be of any other conventional material, including
organic and inorganic materials. Typical substrate materials include insulating non-conducting
materials such as various resins known for this purpose including polycarbonates,
polyamides, polyurethanes, paper, glass, plastic, polyesters such as MYLAR® (available
from DuPont) or MELINEX 447® (available from ICI Americas, Inc.), and the like. If
desired, a conductive substrate can be coated onto an insulating material. In addition,
the substrate can comprise a metallized plastic, such as titanized or aluminized MYLAR®,
wherein the metallized surface is in contact with the photosensitive layer or any
other layer situated between the substrate and the photosensitive layer. The coated
or uncoated substrate can be flexible or rigid, and can have any number of configurations,
such as a plate, a cylindrical drum, a scroll, an endless flexible belt, or the like.
The outer surface of the substrate preferably comprises a metal oxide such as aluminum
oxide, nickel oxide, titanium oxide, and the like.
[0020] The substrate may be of any dimension conventionally employed in photoreceptors.
For example, in embodiments, hollow cylindrical substrates may have an inside diameter
ranging from about 0.7874 inch (20 mm) to about 30 inches (76.2cm), an outside diameter
ranging from about 0.7884 inch to about 30.5 inches (77.5cm), a length ranging from
about 7 to about 44 inches (17.8 to about 111.8cm), and a wall thickness ranging from
about 0.001 to about 4 inches (25.4µm to about 10.16cm).
[0021] The substrate is optionally provided with an anodizing treatment to form a protective
film, e.g., an oxide film, on the substrate surface so that the substrate can be placed
into the subsequent metal deposition bath and the protective film will be inert to
the bath long enough to obtain a metal layer on the substrate. It is understood that
the materials and numerical parameters expressly recited herein for the anodizing
treatment are preferred embodiments and that materials and numerical parameters outside
those expressly recited may be employed. The anodizing treatment may be accomplished
in embodiments by establishing an anodizing zone which comprises a suitable metal
cathode selected, for example, from the group consisting of lead, aluminum, stainless
steel, and lead alloys such as lead/tin. The anode comprises the substrate. The cathode
and the substrate anode are separated by an anodizing bath maintained at a temperature
of from about 60° to about 100°F (about 15.5 to 37°C), and preferably about 78° to
about 80°F (about 25.6 to 32.2°C). A more preferred temperature in embodiments is
79°F (26.1°C). After the substrate anode has been exposed to the bath for an effective
time, preferably from about 1 to about 3 minutes without any voltage applied, then
the voltage is applied gradually. The voltage is raised to about 12 to about 25V,
and preferably to about 15 to 17V over a period of about 1 to about 2 minutes. More
preferably, the voltage is raised to 16V over a period of 1.5 minutes and maintained
at 16V for 13.5 minutes. During this period, sufficient agitation may be imparted
to the anodizing bath to continuously expose the substance anode to fresh anodizing
bath. Preferably, the substrate anode is rotated at 1.5 to 3 rpms in order to obtain
sufficient agitation. The anodizing bath is maintained within the zone at a stable
equilibrium composition comprising for example in embodiments: 2.7 to 3.7 parts conc.
of a suitable acid such as H₃PO₄ to 6.3 to 7.3 parts H₂O. The preferred amount of
H₃PO₄ in the anodizing bath is in the amount of: 3.0 parts H₃PO₄ to 7.0 parts H₂O.
[0022] Subsequently, the substrate anode is removed from the anodizing bath preferably while
the voltage is still being applied to the anodizing bath. The substrate anode may
be rinsed with any suitable solvent such as water to remove the anodizing bath solution
from the substrate anode. A preferred rinsing step is with water at a rate of at least
1.5 to 2 gallons per minute (5.7 to 7.6 l/min) while the substrate anode is rotated
at 7 to 10 rpms for at least 6 complete revolutions. The most preferred rinsing step
at this point is after the substrate has been rinsed as just described, the substrate
is rinsed again with water at a rate of 5 gallons per minute (19l/m) while rotating
the substrate anode at 30 to 40 rpms for 1 to 2 minutes.
[0023] A metal deposition zone is then established which comprises a suitable metal anode
selected from the metals described herein and preferably selected from the group consisting
of nickel and nickel alloy, and a cathode comprising the substrate. It is understood
that the materials and numerical parameters expressly recited herein for the metal
deposition step are preferred embodiments and that materials and numerical parameters
outside those expressly recited may be employed. The substrate cathode and anode are
separated by a metal bath maintained at any effective temperature such as from about
120° to about 160°F (48.9 to 71.1°C), and especially from about 132° to about 138°F
(55.6 to 58.9°C). The preferred temperature is 135°F (57.2°C). A current, i.e. ramp
current, may be applied when the substrate cathode enters the nickel bath of from
about 10 to 20 A/ft² (107.5 to 215 A/m²). A voltage of 3 volts may be applied. The
preferred rotation of the cathode at this point when the substrate cathode enters
the nickel bath is 28 to 32 rpms, while the preferred current density is maintained
at 10 to 20 A/ft² (107.5 to 215 A/m²) and the preferred voltage is maintained at 3V.
Then the current, i.e., ramp current, may be increased over a period of at least 5
seconds, preferably from about 30 seconds to 3 minutes, to about 75 to 300 A/ft² (806.3
to 3225 A/m²). Preferably, at this time the rotation of the substrate cathode is at
36 to 40 rpms after the preferred ramp current is increased to about 75 to 300 A/ft²
(806.3 to 3225 A/m²). The most preferred ramp current increase is where the ramp current
is increased to about 100 to about 200 A/ft² (1075 to 2150A/m²) over a period of 5
seconds to about 2 minutes while the substrate is rotated at 36 to 40 rpms.
[0024] The metal bath is preferably agitated to continuously expose the substrate cathode
to fresh metal bath while maintaining the metal bath within the metal deposition zone
at a stable equilibrium composition comprising in embodiments:
total metal, any suitable metal illustrated herein such as nickel sulfate or nickel
sulfamate, at an effective concentration such as 9 to 11 oz/gal (67.3 to 82.2 g/l),
and preferably 10 oz/gal (74.7 g/l) (the recited concentrations for the total metal
refer to the metal alone without any counterions and does not include the metal component
of the halide compound disclosed herein as NiX₂ · 6H₂O);
halide as NiX₂ · 6H₂O at an effective concentration such as 1.0 to 1.4 oz/gal (7.47
to 10.5 g/l), and preferably 1.2 oz/gal (8.96 g/l);
wherein X is a halogen such as chloride, iodine and bromine; and
a suitable inorganic acid such as H₃BO₃ at an effective concentration such as 4.8
to 5.2 oz/gal (35.9 to 38.9 g/l), and preferably 5 oz/gal (37.4 g/l).
[0025] The surface tension of the metal bath may be thereafter continuously maintained at
about 33 to 42 dynes per cm, and preferably, 38 dynes per cm. The substrate cathode
then may be removed from the metal bath while continuously imparting sufficient agitation
to the metal bath to continuously expose the substrate cathode to fresh bath. The
pH of the metal bath may be, for example, from about 3.6 to about 4.8, preferably
3.8 to 4.3, and most preferably 4.1. The preferred anode to substrate cathode surface
area ratio is 1.5 to 1.
[0026] Thereafter, the substrate may be removed from the metal bath and rinsed with a suitable
solvent such as water, preferably at a rate of about 5 gallons per minute, to remove
the metal bath solution from the substrate cathode.
[0027] Preferably, the metal anodes may be nickel, carbonyl nickel anodes, electrolytic
sulfur depolarized nickel or even carbon or oxygen depolarized anodes.
[0028] Preferably, the substrate cathode is rotated at an effective rate of, for example,
about 28 to 30 rpms using any suitable equipment such as a spindle, bladder, or gripping
fingers coupled to an motor drive unit which has a gear reduction system capable of
rotating the substrate. The substrate cathode is then removed from the nickel bath.
[0029] The preferred rinsing procedure after metal deposition comprises contacting the substrate
cathode with water at an effective rate of, for example, 1.5 to 2 gallons per minute
(5.7 to 7.6 l/min) while the substrate cathode is being rotated at 7 to 10 rpms for
at least 6 complete revolutions. The most preferred rinsing step to remove the nickel
bath comprises rinsing the substrate with water at a rate of 5 gallons per minute
(19 l/m) while rotating the substrate cathode at 30 to 40 rpms for 5 to 10 minutes.
[0030] In other embodiments, it is believed that the substrate may be metal coated by any
other suitable technique such as vacuum deposition and electroless deposition. Various
electroless metal deposition processes are illustrated, for example, US-A-4,666,735
and US-A-3,632,435. Although the electroless deposit of metal may be accomplished
in embodiments without the creation of metal nucleating sites on the substrate surface,
such nucleating sites are preferred to facilitate the subsequent electroless deposit
of the metal. Metal nucleating sites may be created by any suitable process including
coating of a colloidal material, in an effective amount, onto the substrate surface
to further the sensitization or activation of the same for the electroless metal deposition.
The colloidal material applied to the substrate may be selected from colloids conventionally
used in the activation of a support for electroless deposition. As described hereafter,
the activation of the substrate may be conducted in one or more steps.
[0031] When a one step activation procedure is utilized, the surface of the substrate is
contacted with an acidic aqueous bath containing an effective amount of a mixture
of a noble metal salt and a reducing agent for the noble metal cation. A colloidal
material which is catalytic to the metal to be deposited is coated upon the surface
of the substrate. Illustrative examples of such baths from which the catalytic colloid
may be applied are disclosed in US-A-3,011,920.
[0032] In embodiments, a variation of the single step activation procedure may be employed
using an acceleration step such as that illustrated in US-A-3,011,920. A substrate
sensitizer containing, for example, stannous chloride was combined with palladium
chloride to form a colloidal dispersion of a catalytic metal. Stannous chloride in
the combined system also may act as a protective colloid for the catalyst, stabilizing
the catalyst against agglomeration and premature precipitation. Excess stannous ions
relative to palladium ions may stabilize the catalyst. An optional acceleration step
may remove the protective colloid from the catalyst metal after the catalyst metal
has been deposited on the substrate and prior to deposition of the conductive metal.
The acceleration step may use an effective amount of, for example, an alkaline material
or preferably a dilute acid, such as hydrochloric acid, wherein the acceleration step
is believed to lead to stronger adsorption and bonding of the conductive metal to
the substrate.
[0033] Alternatively, an effective amount of a colloidal material such as a metallic salt,
capable of reducing a noble cation, e.g., a colloidal stannous salt, may initially
be applied from a bath containing the same to coat the substrate. While such a metallic
salt alone may be not generally catalytic to the metal which is to be applied, it
may subsequently be contacted with an additional bath containing an effective amount
of a salt of a noble metal, and the substrate accordingly activated as the cation
of the noble metal salt is reduced and deposited upon the substrate at the same location
previously occupied by the colloidal metallic salt prior to the oxidation of the cation.
[0034] The colloidal metallic salt which is applied to the surface of the substrate is lyophobic,
and preferably hydrophobic. Stannous salts, such as stannous chloride (SnCl₂), are
preferred colloidal materials commonly used in the preparation of a substrate for
electroless deposition. Such colloids in effective amounts may be applied to a substrate
while suspended in a dilute aqueous hydrochloric acid solution. A colloidal metallic
salt, such as a stannous chloride, serves to prepare the surface of the substrate
to receive a noble metal. Upon contact with the surface of the substrate, a coating
or film of a colloidal material is effectively deposited thereupon. When the surface
of the substrate is negatively charged, the colloidal film is not merely deposited
thereon, but is electrically attached to the surface.
[0035] It is understood that nucleating sites may be created by the use of effective amounts
of a noble metal, stannous salts, or mixtures thereof, and the like. In embodiments,
stannous salts can form nucleating sites without the use of noble metal salts. Noble
metal cations include gold, silver, platinum, palladium, iridium, rhenium, mercury,
ruthenium, or osmium, and the like. Suitable counterions to the noble metal cations
include acetate and halogens such as chloride and bromide, and the like.
[0036] Representative metals that may be used to coat the substrate include tin, aluminum,
iron, steel, nickel, copper, gold, silver, platinum, palladium, mixtures thereof,
and the like.
[0037] In embodiments, the metal layer deposited on the substrate may be of any effective
thickness, preferably ranging from about 10 microns to about 5 mm, and more preferably
from about 10 to about 100 microns.
[0038] In embodiments, the substrate surface is marred by at least one surface blemish,
and preferably a plurality of surface blemishes. In embodiments, the layer of metal
deposited on the substrate has a surface appearance which conceals at least a portion
of the underlying substrate surface blemish or blemishes, and preferably conceals
all of the underlying blemishes. The term "conceals" indicates that the surface appearance
of the portion of the metal layer overlying the blemish is virtually indistinguishable
from the surface appearance of the metal layer overlying an unblemished portion of
the substrate surface. In certain embodiments, at least a portion, and preferably
all of the surface blemishes are removed prior to the deposition of the metal layer.
Removal may be accomplished by any suitable technique including machining away the
blemishes using, for example, a lathe to rotate the substrate and a cutting tool to
remove the blemishes. Removal of the surface blemishes may decrease the substrate
dimensions to an extent where the substrate is unacceptable for use as a photoreceptor
substrate In such situations, sufficient metal may be deposited on the substrate to
increase the dimensions thereof to render the substrate suitable for use as a photoreceptor
substrate.
[0039] In certain embodiments, there is provided a photoreceptor substrate wherein the substrate
surface is marred by at least one blemish, wherein the blemish is a surface height
defect. A layer of metal having a thickness as disclosed herein is deposited on the
substrate surface to cover at least the blemish, wherein the metal layer has a surface
appearance which reflects the underlying substrate surface blemish, thereby resulting
in a metal layer marred by at least one surface blemish. Subsequently, at least a
portion of the blemish appearing on the surface of the metal layer is removed, and
preferably without exposing the underlying substrate surface. Removal may be accomplished
by any suitable technique including machining away the blemishes using, for example,
a lathe to rotate the substrate and a cutting tool to remove the blemishes.
[0040] In embodiments, the deposited metal layer has a surface roughness which is effective
for substantially reducing the plywood effect. The metal layer, deposited by the methods
disclosed herein, may have in embodiments the requisite plywood suppression surface
morphology without a further surface roughening treatment. For example, US-A-5,096,792,
discloses metal deposition processes which form the ground plane surface with a rough
surface morphology effective for suppressing the plywood effect. In certain embodiments,
a separate surface roughening step is employed to obtain the plywood suppression surface
morphology using any effective technique including those illustrated in US-A-4,618,552,
such as the sand blast method, the brush polishing method and the anodic oxidation
method
[0041] The roughness of a particular surface may be defined by several parameters, R
a (mean roughness), R
q (root mean square), R
t (maximum roughness depth), R
pm (mean levelling depth), W
t (waviness depth), and P
t (profile depth), the definitions of which are well known. R
a is the arithmetic average of all departures of the roughness profile from the mean
line within the evaluation length and in embodiments may be any value effective for
substantially suppressing plywood, preferably ranging from about 0.05 to about 0.7
µm, more preferably from about 0.1 to about 0.6 µm, and most preferably from about
0.10 to about 0.55 µm. In embodiments, R
a has a value of from about λ/4N to about λ/2N, wherein λ is the wavelength of the
light source which is directed (scanned) across the surface of the photoreceptor and
is from about 600 nm to about 900 nm, preferably from about 700 nm to about 800 nm,
and N is an optical index of the photosensitive coatings and has a value from about
1 to about 3, and preferably from about 1.2 to about 2.0. R
q is the geometric average of all departures of the roughness profile from the mean
line within the evaluation length and in embodiments may be any value effective for
substantially suppressing plywood, preferably ranging from about 1 to about 6 µm,
and more preferably from about 2 to about 3 µm. R
t is the vertical distance between the highest peak and the lowest valley of the roughness
profile R within the evaluation length and in embodiments may be any value effective
for substantially suppressing plywood, preferably ranging from about 0.5 to about
6 µm, and more preferably from about 0.8 to about 4.5 µm. R
pm is the mean of five levelling depths of five successive sample lengths and in embodiments
may be any value effective for substantially suppressing plywood, preferably ranging
from about 0.2 to about 2 µm, and more preferably from about 0.3 to about 1.5 µm.
W
t is the vertical distance between the highest and lowest points of the waviness profile
W within the evaluation length and in embodiments may be any value effective for substantially
suppressing plywood, preferably ranging from about 0.1 to about 1 µm, and more preferably
from about 0.15 to about 0.5 µm. P
t is the distance between two parallel lines enveloping the profile within the evaluation
length at their minimum separation and in embodiments may be any value effective for
substantially suppressing plywood, preferably ranging from about 0.8 to about 6 µm,
and more preferably from about 1 to about 4 µm. Significant plywood suppression may
be observed in embodiments of the present invention at the light source wavelengths
conventionally used, including a light source having a wavelength at 780 nm.
[0042] It is understood that in embodiments, even in plywood suppressing ones, the surface
morphology of the substrate may be characterized by one or more, but not necessarily
all, of the specified values recited for the various surface roughness parameters
disclosed herein.
[0043] The surface roughness parameters, R
a, R
q, R
t, R
pm, W
t, and P
t, can be determined by a Perthen Surface Profilometer Model #S8P, available from Mahr
Feinpruef Corp., by utilizing a 5 µm radius contact probe which rides over the surface
and directly, by contact, measures the surface contour. An alternate attachment for
the Perthen Surface Profilometer Model #S8P can measure the surface by projecting
a laser beam onto the surface and measuring the change in focal length observed as
the beam scans across the surface. It is understood that other devices and methods
equivalent to those disclosed herein may also be employed to measure the various surface
roughness parameters.
[0044] After the metal coated substrate is formed, one or more layers are deposited in succession
thereon to prepare the photosensitive imaging member. The composition and deposition
of these additional layers are known to those skilled in the art. For example, one
or more photosensitive layers are typically deposited on the substrate. In embodiments,
a charge transport layer such as an arylamine, reference for example US-A-4,265,660,
and a charge generating layer comprise the photosensitive layers. This is referred
to as a laminate or layered type photosensitive material. Charge transport and charge
generating layers may be deposited by any suitable conventional technique including
dip coating and vapor deposition and are well known in the art as illustrated for
example in US-A-s4,390,611; 4,551,404; 4,588,667; 4,596,754; and 4,797,337. In embodiments,
the charge generation layer may be formed by dispersing a charge generating material
selected from, for example, azo pigments such as Sudan Red, Dian Blue, Janus Green
B, and the like; quinone pigments such as Algol Yellow, Pyrene Quinone, Indanthrene
Brilliant Violet RRP, and the like; quinocyanine pigments; perylene pigments; indigo
pigments such as indigo, thioindigo, and the like; bisbenzoimidazole pigments such
as Indofast Orange toner, and the like; phthalocyanine pigments such as copper phthalocyanine,
aluminochloro-phthalocyanine, and the like; quinacridone pigments; or azulene compounds
in a binder resin such as polyester, polystyrene, polyvinyl butyral, polyvinyl pyrrolidone,
methyl cellulose, polyacrylates, cellulose esters, and the like. In embodiments, the
charge transport layer may be formed by dissolving a positive hole transporting material
selected from compounds having in the main chain or the side chain a polycyclic aromatic
ring such as anthracene, pyrene, phenanthrene, coronene, and the like, or a nitrogen-containing
hetero ring such as indole, carbazole, oxazole, isoxazole, thiazole, imidazole, pyrazole,
oxadiazole, pyrazoline, thiadiazole, triazole, and the like, and hydrazone compounds
in a resin having a film-forming property. Such resins may include polycarbonate,
polymethacrylates, polyarylate, polystyrene, polyester, polysulfone, styrene-acrylonitrile
copolymer, styrene-methyl methacrylate copolymer, and the like.
[0045] In embodiments, the photosensitive material may be of a single-layer type comprising
the charge generating material, charge transporting material, and the binder resin,
wherein these three materials may be as described above. Single layer type photosensitive
materials may be deposited by any suitable technique including dip coating and vapor
deposition and are illustrated, for example, in US-A-5,004,662 and US-A-4,965, 155.
[0046] The invention will now be described in detail with respect to specific preferred
embodiments thereof, it being understood that these examples are intended to be illustrative
only and the invention is not intended to be limited to the materials, conditions
or process parameters recited herein. All percentages and parts are by weight unless
otherwise indicated.
EXAMPLE 1
[0047] A cylindrical, hollow aluminum substrate, approximately 38 mm in (inside) diameter,
about 40 mm in (outside) diameter, about 338 mm in height and walls approximately
1 mm thick, is provided. The substrate surface is marred by a plurality of surface
nicks and scratches having a depth less than or equal to 0.076 mm. To remove all of
the surface blemishes, the substrate is machined down by about 0.080 mm using a lathe
to rotate the substrate at about 20,000 feet per minute (6100 m/min) and employing
a diamond cutting tool. The surface of the machined substrate is thus rendered smooth
without any visible defects such as nicks, scratches and tool marks. The surface of
the substrate has a R
q value ranging from about 1 to about 6 µm. The substrate is blown free of grit or
dirt or any foreign material which might cause damage. The substrate is therefore
cleaned by washing with acetone to remove any oil and the like. Then those surfaces
which are not to be plated are masked. The masking material must be non-reactive with
the subsequent plating baths. The ends of the substrate must be plugged or masked
so that the inside of the substrate is not plated. The substrate is hooked up to a
hoist so that the substrate can be moved between the various baths. The substrate
is mounted such that the mounting apparatus and substrate can be rinsed so that all
the material on the substrate and mounting, i.e., the previous bath, can be removed
by rinsing before entering a subsequent bath. The ends of the substrate are connected
to "robbers". The "robbers" steal plating from the ends of the substrate during the
plating operation ensuring that the plating on the edges which may be the same as,
i.e thickness, the plating in the center of the substrate. The "robber" is such so
it can be completely rinsed.
[0048] The substrate is given another complete cleaning. Acetone is applied to the surface
of the substrate by a squirt bottle to wet the surface of the substrate, then the
surface is wiped with a litho wipe such as a paper cloth, which is damp with acetone.
This removes any organic contaminates.
[0049] The substrate is then scrubbed to further clean the surface, by for example, chemically
cleaning.
[0050] The substrate's surface is scrubbed with a nylon pad, i.e., Scotch Brite®, and alpha
alumina. The alpha alumina is very fine about 0.3 µm.
[0051] Subsequently, the substrate is scrubbed with a soft material, such as paper cloth
and then alpha alumina. The substrate is completely scrubbed in both directions.
[0052] All traces of the alpha alumina are removed. This is done by flushing the substrate
with deionized water while rubbing the surface with clean litho wipes until all the
alpha alumina is gone. The substrate is rubbed with the litho wipes until there is
no black obtained on the litho wipes. During this process, deionized water is cascaded
over the substrate.
[0053] The substrate is moved to the anodizing bath. The bath is 3 parts 85% H₃PO₄ to 10
parts deionized water. The temperature of the bath is about 79°F (26.1°C). The bath
is about 140 gallons (532l) in a gallon tank. The cathode is of lead and the cathode
to anode, i.e. substrate, surface area ratio is 1 to 1. The substrate enters the bath,
with no voltage applied to the bath. The substrate is wet from the deionized water
rinse. The substrate stands in the anodizing bath for 2 minutes while slowly rotating
at about 2.5 rpms, and the voltage is increased slowly and not allowed to exceed 17V.
The substrate remains in the anodizing bath for about 15 minutes. The voltage is at
16V. The substrate is removed from the anodizing bath while the voltage is still being
applied. A "full rinse" is initiated as soon as the substrate clears the tank to ensure
that all the residue of the previous bath is removed from the substrate before the
substrate enters the next bath.
[0054] A "full rinse" is given to the substrate. The "full rinse" begins with step I where
deionized water is directed from a 3/4 inch pipe at about 1.5 to 2 gallons per minute
(5.7 to 7.6 l/min) onto the substrate. The substrate is being rotated from about 7
to 10 rpms. This is continued for at least 6 complete revolutions. Then step II is
accomplished where the flow of water is increased to about 5 gallons (19 l/min) per
minute while rotating the substrate at about 30 to 40 rpms. Then step I is repeated.
After this, the substrate is slowed to 7 to 10 rpms while rinsing with deionized water
at 1.5 to 2 gallons per minute (5.7 to 7.6 l/min). Then the water is directed at about
1.5 to 2 gallons per minute (5.7 to 7.6 l/min) while the substrate is rotated at about
7 to 10 rpms to specific parts of the substrate, the mounting apparatus and the like,
in order to assure that all the crevices are free of any residue from the anodizing
bath. The "robber rings" and mounting apparatus should be free of any anodizing bath
residue.
[0055] The substrate is moved to the nickel bath while it is still wet from the rinse step.
The nickel bath is in a 180 gallon (684l) tank with 170 gallons (646l) of nickel bath.
The bath is (1) nickel at a concentration of 10 oz/gallon (74.7 g/l), (2) NiCl₂·6H₂O
at a concentration of 1.2 oz/gallon (8.97 g/l), (3) H₃BO₃ at a concentration of 5
oz/gallon (37.4 g/l). The surface tension is about 38 dynes per cm. The pH is about
4.1. The temperature is about 135°F (57.2°C). The anode is nickel. The anode to cathode,
i.e. substrate, surface area ratio is 1.5 to 1.
[0056] The substrate enters the nickel bath while the voltage is applied. The substrate
is rotating at about 30 rpms. The voltage is about 3V at 15A. As soon as the substrate
is completely in the bath, the rotation of the substrate is increased to 35 rpms.
The ramp current is increased over a period of 60 seconds from about 15 to about 200
A/ft² (161 to 2150 A/m²). The bath is continuously filtered with a skimmer to remove
residue from the top of the bath. The amount of time in the nickel bath depends upon
the final desired diameter of the substrate. Here, the substrate stays in the plating
bath long enough to increase the substrate diameter by about 0.080 mm of nickel. The
final outside diameter of the nickel coated substrate is about 40 mm. After the plating
is completed, the substrate is slowly rotated at about 29 rpms during removal from
the nickel bath. The "quick rinse" is initiated as soon as the coated substrate starts
to clear the nickel bath. The "quick rinse" is the same as step I of the "full rinse"
described previously in this example.
[0057] The resulting metal coated substrate has a surface roughness characterized by one
or more of the following parameters which can be determined by a 5 µm radius stylus
used on a Perthometer Model #S8P available from Mahr Feinpruef Corporation: R
a having a value ranging from about 0.05 to about 0.7 µm; R
q having a value ranging from about 1 to about 6 µm; R
t having a value ranging from about 0.5 to about 6 µm; R
pm having a value ranging from about 0.2 to about 2 µm; W
t having a value ranging from about 0.1 to about 1 µm; and P
t having a value ranging from about 0.8 to about 6 µm.