U.S. patent number 3,848,305 [Application Number 05/317,975] was granted by the patent office on 1974-11-19 for roll for contact fusing thermoplastic particles to substrates.
This patent grant is currently assigned to International Business Machines Corporation. Invention is credited to Paul D. Jachimiak.
United States Patent |
3,848,305 |
Jachimiak |
November 19, 1974 |
ROLL FOR CONTACT FUSING THERMOPLASTIC PARTICLES TO SUBSTRATES
Abstract
A fuser roll is coated with a silicone elastomer and heat and
vacuum cured to remove the cyclic siloxanes to a state of constant
weight loss to improve the release of paper and toner from the roll
surface.
Inventors: |
Jachimiak; Paul D. (Lexington,
KY) |
Assignee: |
International Business Machines
Corporation (Armonk, NY)
|
Family
ID: |
23236084 |
Appl.
No.: |
05/317,975 |
Filed: |
December 26, 1972 |
Current U.S.
Class: |
492/56; 427/350;
427/377; 427/387 |
Current CPC
Class: |
G03G
15/2057 (20130101); C08G 77/32 (20130101) |
Current International
Class: |
B29C
35/02 (20060101); B29C 70/00 (20060101); B29C
70/68 (20060101); C08G 77/00 (20060101); C08G
77/32 (20060101); G03G 15/20 (20060101); B21b
031/08 () |
Field of
Search: |
;29/132,129.5,130 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Guest; Alfred R.
Attorney, Agent or Firm: Letson; Laurence R.
Claims
I claim:
1. A roll for fusing thermoplastic granular material to a
substrate, said roll having a cylindrical core, and a coating on
said core of a silicone elastomeric material, the improvement
comprising:
said coating having the volatile components thereof, reduced to a
level at which the coating has, under in service conditions, a
substantially constant rate of weight loss.
2. A roll for fusing thermoplastic granular material to a
substrate, said roll having a cylindrical core, and a coating on
said core of a silicone elastomeric material, the improvement
comprising:
said coating having the volatile components thereof, reduced to
below the level at which said coating has a substantially constant
rate of weight loss for a selected temperature and under a selected
nip pressure.
3. The roll of claim 2 wherein said volatile components are cyclic
siloxanes having the basic unit structure of ##SPC5##
where n equals to 3 to 8.
Description
BACKGROUND OF THE INVENTION
This invention relates to the field of electrophotographic
reproduction and more particularly to the field of fusing of
thermoplastic toner particles to a porous substrate such as paper
in order to render the copies produced by the electrophotographic
process, permanent.
Several different techniques have been used in the past to fuse or
fix the thermoplastic powder material used to develop
electrophotographic images. For example, the thermoplastic powder
or toner can be fused by radiant heating, vapor fusing, conductive
heating through the paper and fuser roll techniques such as hot
rolls or high pressure rolls.
Within the fuser roll technique, there has been two different
approaches, that being the use of a rigid, or non-deforming hot
roll and a compliant back-up roll and the other technique being the
use of a rigid back-up roll and a compliant hot roll. In either
case the roll which is compliant is generally a sturdy rigid
cylinder which is in turn coated with a layer of an elastomeric
material which then is deformed in the pressure nip formed by it
and its mating roll in the fuser roll apparatus, thus creating a
footprint or width where the two roll surfaces intimately engage.
This footprint or nip is necessary due to the fact that two rigid
rolls engaging each other would only provide line contact or at
best a very very narrow contact when engaging the paper and there
would be insufficient residence time in which to transfer enough
thermal energy to the toner to adequately soften and fuse the toner
particles to the paper. If very high loads are applied to rolls
with elastomer coating such as to simulate two high pressure
metallic rolls, then the elastomer is subject to premature failure
due to the very high stresses applied to the elastomer.
The preferable arrangement within fusing apparatuses implementing
the fuser roll technique, is to use a deformable or elastomeric
coated fuser hot roll and a relatively rigid back-up roll.
Prior art fuser rolls have been coated with silicone elastomers and
in some cases further encased in sleeves of low surface energy
materials which do not contain cyclic siloxanes. Other approaches
to the release problem include use of low energy fillers such as
polytetraflouroethylene. Other fuser rolls use a higher energy
level material and apply a release material in liquid form to
offset deleterious effects of the higher energy materials, or
release properties.
For clarity, the term hot roll, as used herein, may be
interchangeably used with that of fuser roll and designates the
roll which is heated and is forced into engagement with the surface
of the paper carrying the unfused toner image.
The term back-up roll is used in the sense that it engages the
reverse side of the sheet from that carrying the unfused toner
image and provides the backing force for the paper to cause
intimate engagement between the hot roll surface and the toner
image.
The deformable or elastomeric coated hot roll is preferable because
the radius of the roll surface, when deformed, is a much sharper or
shorter radius at the exit point of the nip than the undeformed
radius of the roll. This sharp curve or shortened radius is
beneficial to release of the copy from the surface of the hot roll
since it is very difficult for the toned paper to traverse the
short radius thus staying with and wrapping to the hot roll causing
a paper feed failure.
Release, and the attendant propensity for wrapping of the copy
around the hot roll, is a problem which has plagued hot roll fusing
since its inception. This is due to the fact that in order to fuse
the toner, the toner must be made soft, tacky, and partially melted
to effect fusing and therefore it has a tendency to offset or stick
to the surface of anything with which it comes in contact. Because
of this tendency of sticking or offset of the toner material to any
surface with which it comes in contact while in a soft tacky state,
it is necessary to use materials in the hot roll construction which
have a very, very low surface energy or have a low tendency to
stick to other materials.
It has been discovered that silicone rubbers have a very low
surface energy and are generally of the class of materials which
are advantageous in this implementation. Unfortunately, silicone
rubbers have several qualities which have prevented wide-spread
commercialized use as roll fuser coatings. The silicone rubbers
have a very low surface energy at room temperature; however, when
raised to elevated temperatures for the operation of the roll
fuser, the silicone rubbers release properties are greatly
deteriorated. Because of the deterioration of the release
properties, paper and toner images have a tendency to adhere to the
roll and wrap around the roll causing a fuser failure.
This type of failure, it is believed, can be caused by materials in
the roll which are adversely effected by the temperatures at which
the roll is operated resulting in degradation of release qualities
of the roll at elevated temperatures.
It is the primary object of this invention to remove cyclic
siloxanes from the elastomeric coating material to extend the
useful life of a hot roll within a roll fusing apparatus.
It is an object of this invention to improve hot roll fusing.
It is another object of this invention to improve release of copies
and images from the roll of a hot roll fuser.
It is an additional object of this invention to cure the
elastomeric coating material of the hot roll to facilitate release
of copies and images.
It is an important object of this invention to remove cyclic
siloxanes to enhance copy release from the surface of the
elastomeric material.
SUMMARY OF THE INVENTION
The shortcomings of the prior art are overcome together with the
accomplishment of the above objects by the removal of cyclic
siloxanes from elastomeric silicone rubber materials used as hot
roll fuser coatings. The cyclic siloxanes are removed by a
simultaneous, combination treatment of heating the coated roll
structure to a temperature above the normal operating temperature
of the roll and subjecting the roll and coating to a high vacuum
during the heating process. This accelerates the removal of cyclic
siloxanes and enhances the breakdown by any metastable crosslinks
which would otherwise result in cyclic siloxanes liberation later
in service in the fuser apparatus thus adversely effecting
release.
A more detailed understanding of the invention will become apparent
from the detailed description to follow, and the drawing.
The FIGURE is a general curve illustrating the weight loss with
time at a temperature for a silicone elastomer.
DETAILED DESCRIPTION
For the sake of illustration of the preferred embodiment, the
description of materials and procedures will be made with respect
to a silicone rubber material manufactured and sold by General
Electric Corporation designated as RTC-60. Other silicone rubbers
behave in the same or similar manner and the procedures taught
herein are believed to be applicable to them.
This material is made-up of four constituents pre-combined in one
container. The basic or main constituent of the RTV-60 is
polydimethyl siloxane with approximately 1,000 Si-O units per a
linear chain. ##SPC1##
The above material is of the general form where n equals
approximately 1,000. Contained in this material are two filler
materials, a first filler material of silicon dioxide (SiO.sub.2)
and a second filler material ferric oxide (Fe.sub.2 O.sub.3). In
addition to the above three constituents, a fourth constituent is a
trifunctional silane of the form ##SPC2##
where R is an organic group.
As a separate material, dibutyltin dilaurate catalyst is provided.
The dibutyltin dilaurate catalyst is added to the four constituents
listed above, to initiate the vulcanization or crosslinking of the
basic composition. As the vulcanization or crosslinking progresses,
an elastomeric, network structure is formed.
Due to incomplete crosslinking or vulcanization, there are formed
quantities of cyclic siloxanes of the general formula ##SPC3##
where n ranges from 3 to 8, and where the structure is formed into
a ring. As an example, the cyclic siloxane wherein n equals 4 is
illustrated below: ##SPC4##
The cyclic siloxanes are present as an impurity in the crosslinked
polymer and also are formed by degradation of the polymeric
crosslinked structure with thermal aging. The chains in the
crosslinked structure, by natural phenomena, have some bonds which
are weaker than others. When the material is heated, energy is
provided by which these bonds may be broken and a segment of the
longer chain is then separated from the crosslinked structure and
continues to break down until such time as n of the general formula
for cyclic siloxanes is in the range of from 3 to 8. At elevated
temperatures these materials are then chemically stable and exist
in either a liquid or vapor state depending on their individual
melting and boiling points and the prevailing conditions. The
cyclic siloxanes have varying boiling points depending on the
molecular weights. Some boiling points are sufficiently high that
it is necessary to reduce the pressure to a vacuum to volatilize
these materials rapidly enough to prevent a build-up of these
products. The boiling points are set forth in Table I below.
TABLE I ______________________________________ BOILING POINTS OF
CYCLIC SILOXANES AT SPECIFIED PRESSURES
______________________________________ n Boiling Point .degree.F
Pressure in mm Hg. ______________________________________ 3 271 760
4 340 760 5 400 760 6 456 760 7 297 20 8 334 20
______________________________________
As one may observe, the cure temperature must be above the
operating temperature of the roll, preferably above the highest
boiling point of the material to be removed. Thus, under a pressure
of about 20 mms of Hg the cure temperature should be above
334.degree.F. The temperature of a roll in operation is
approximately 340.degree. to 380.degree.F. A temperature of cure of
500.degree.F. is both adeugate and high enough to provide
efficiency of speed when coupled with a vacuum pressure of about 20
mm Hg.
It has been discovered that the cyclic siloxanes present in the
polymer and formed as degradation products are apparently
detrimental to release properties of the silicone rubber coating.
These cyclic siloxanes are very similar in general structure to
materials which have been known as release agents, for example, Dow
Corning 200 silicone liquid which is a polydimethylsiloxane. The
primary difference is that the cyclic siloxanes have a detrimental
effect on the surface characteristics of the silicone rubber. The
cyclic siloxanes have a tendency to make the rubber tacky or sticky
whereas it generally has a relatively low surface energy level and
thus would not be tacky, sticky, or adherent. The prior art teaches
the use of polydimethylsiloxanes as release agents, but these are
taught with materials other than the silicone rubbers. Examples are
the use of polydimethylsiloxanes either on steel rolls or on a
Teflon (Trademark of DuPont Corporation) surface. It becomes
apparent from the difference in performance, that although these
cyclic siloxanes may in some environments have a beneficial effect,
in the present environment of a dry silicone elastomer hot roll, a
deliterious effect is observed.
As temperature increases in the roll and coating, the weak bonds of
the structure will break and the cyclic siloxanes will form adding
to any cyclics in the original polymer. As they form, their state
changes to a liquid or vapor depending upon the number of Si-O
units in the particular siloxane and also the temperature at which
the material is maintained.
It has been discovered that the removal of the cyclic siloxanes
which are present after the vulcanization phase of preparation
along with those formed at elevated service temperatures at which
hot rolls must of necessity operate due to the breaking of
metastable crosslinks, is beneficial to the release properties of
the roll and thus extends the life of the roll to the point where a
silicone rubber coated roll is economically and functionally
feasible. The procedures for rapid removal and curing of the roll
are best understood by following the fabrication procedure from the
initial phases.
A roll core is fabricated to the desired dimensions and mounted in
a lathe. The RTV-60 silicone material is catalyzed using the
dibutyltin dilaurate catalyst up to approximately 0.50 percent by
weight. This mixture is then doctored onto the roll as the roll is
revolved by the lathe, yielding a coating 30 to 60 mils in
thickness. The roll is then continued to be rotated and cured at
room temperature for approximately 24 hours. After the 24 hour
curing at room temperature, the roll temperature is elevated to
approximately 150.degree. F. for a four hour period to insure
substantially complete vulcanization. After heat treating at
150.degree.F. for four hours, the coating of silicone rubber is
ground to about a 25-50 mil thickness.
After grinding to the desired thickness of coating, the roll is
placed in a vacuum oven and the temperature of the roll is elevated
to approximately 500.degree. F. for a period of 24 hours. The
vacuum oven is operated at approximately 29 inches of Hg
vacuum.
Insofar as the invention is fully understood, it's believed that
the high temperatures of approximately 500.degree. F., being
substantially above the normal operating temperature of the hot
roll, drives off as vapor the cyclic siloxanes which are the
reaction residue of the crosslinking action as well as any cyclic
siloxanes which were present in the original polymer. Additionally,
the temperature at which the roll is maintained, breaks any weak
bonds in the crosslinked structure of the silicone elastomeric
material, thus forming additional cyclic siloxanes. The bonds which
are broken are those which are least stable and which would break
most easily upon the normal heating of the hot roll during
operation. The high vacuum which is imposed upon the roll during
the heating, assists the heat in volatilizing the cyclic siloxanes
and removing them from the rubber roll. It is necessary to rapidly
remove the cyclic siloxanes by the heating and vacuum procedure to
effectively remove those cyclic siloxanes with the higher molecular
weights as they are formed. Otherwise the cyclics are formed and
are slow to dissipate thus building at least an increased transient
level of cyclic siloxanes which is detrimental to continued
reliable performance.
In subsequent work performed with rolls fabricated according to the
above example, it has been found that the simultaneous heat and
vacuum treatment of the coated roll structure, produces a
satisfactory roll when the cyclic siloxane level is reduced to a
point where the cyclic siloxanes are removed at substantially the
same rate as they are formed.
This condition is best described with respect to the weight loss of
the roll, as it is treated or operated. A characteristic of the
silicone rubber elastomeric material formed by the vulcanization of
RTV-60 and other silicone elastomer materials is that as long as
the structure is subject to heat, some polymeric degradation will
occur and cyclic siloxanes form. Thus it is impossible, under
present technology, to remove all cyclic siloxanes and prevent
further formation of these materials when the elastomeric structure
is subjected to elevated service temperatures. FIG. 1 is a general
graph of weight loss as a function of time at a preselected
temperature and pressure for a sample of RTV-60. The region of the
curve, in FIG. 1, indicated as 10 illustrates what can be
characterized as a transient condition during the period of time
when the residual products of vulcanization or crosslinking
specifically the cyclic siloxanes are being removed and during
which time the temperature of the curing process is generating
additional cyclic siloxanes due to the breakage of the weakest or
metastable polymeric bonds of the crosslinked elastomeric material.
Region 12 of the curve is the region at which stabilization occurs
and the rate of removal is reduced due to the fact that excessive
residual vulcanization products are no longer available for removal
and that the only materials remaining for removal are those being
generated on a continuing basis due to the elevated service
temperature.
Region 14 of the curve illustrates the steady state condition which
is accomplished as a result of the removal of the vulcanization
products and the originally produced cyclic siloxanes due to an
initial temperature increase. The generation of cyclic siloxanes
through degradation of the basic elastomeric layer has been
stabilized to a constant rate and the region of the curve in FIG. 1
designated 14, can best be described mathematically as d(WT
loss)/dt = K. The derivitive of weight loss with respect to time
yields a constant after the transient cyclic siloxanes have been
removed.
The constant rate of weight loss may be secured under service
conditioned by either attaining the constant rate under care, or
curing to a high enough point on the curve in either region 10 or
12 that under a reduced service temperature and atmospheric
pressure the rate of weight loss in service is substantially
constant.
It is in that state or condition represented by region 14 where
acceptable and reliable release properties of the roll fuser can be
obtained. During cure, the rate of weight loss in regions 10 and 12
may be increased by higher elevations of temperature and/or an
increase in the vacuum applied. A decrease in vacuum and/or
temperature will decrease the rate of weight loss in these regions
10 and 12 conversely.
The curve is a general one and with appropriate scale would be
applicable to a roll under treatment or in service.
For satisfactory removal of the cyclic siloxanes to insure reliable
initial use and extended life, it is necessary to apply both a
temperature equal to or greater than the normal operating
temperature of the fuser roll and at the same time apply the
vacuum.
The simultaneous treatment is necessary because the application of
vacuum alone will only withdraw those cyclic siloxanes which are in
a liquid or vapor state under normal room temperatures which are
those of the lower molecular weight while leaving uneffected the
higher molecular weight cyclic siloxanes.
Similarly the application of heat alone, especially at extremely
high temperatures, tends to degrade the rubber into the easily
formed cyclic siloxanes while relying purely on volatilization at
atmospheric pressure to drive off these materials. The rate of
vaporization of the cyclic siloxanes is relatively low when
compared with other highly volatile materials and thus a large
quantity of cyclic siloxanes can be formed within the rubber
without their adequate removal when no vacuum is employed together
with the elevated temperature curing.
The foregoing explanation and example has been relative to the
General Electric silicone rubber material marketed under the
designation RTV-60. It should be recognized that other similar
materials are available from other vendors and that they are of the
same general type of materials, ie., that of a long chain silicone
elastomer. The major variation between one vendor's silicone rubber
and another vendor's silicone rubber is generally in the use of
either different amounts or types of filler materials in lieu of
the Fe.sub.2 O.sub.3 and the SiO.sub.2 fillers in the present
illustrations. These materials generally have little or no effect
on the polymerization and are actually only physical fillers. They
do effect thermal properties and other physical properties and
effect the rate of formation of cyclic siloxanes. The exact
conditions of curing for each particular material and the optimum
curing conditions for any particular material will depend upon, (1)
the amount of time available for curing, (2) the operating
temperature of the fusing roll in its normal operating environment,
(3) the particular type of silicone elastomer used. The important
point is that the rate of weight loss for the silicone material
must stabilize at approximately a constant before an equilibrium
state is reached and it is in that state that the enhanced
properties referred to above are most reliably found.
It may be possible in some cases to secure the properties of good
release in that portion of the curve designated as region 12 or
referred to as the knee of the curve, in as much as the cyclic
siloxane level in the material has been reduced to a relatively low
level. It is not possible to determine percentage levels of cyclic
siloxanes with normal laboratory equipment and testing techniques
and therefore the rate of weight loss is used as a definitive
measure of the structure of the materials involved which have
material effects on performance in the hot roll fusing art.
* * * * *