Triboelectrically charging member

The disclosure relates to a triboelectrically charging member including a surface formed with an amorphous carbon film containing at least carbon, hydrogen and fluorine atoms. The amorphous carbon film is formed by plasma polymerization with a glow discharge method. The triboelectrically charging member of the present invention has high hardness, is excellent in friction resistance and can retain a good copy image quality over time.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a triboelectrically charging member. 
2. Description of the Prior Art 
Triboelectrically charging members are used in a variety of fields and are 
generally desirable due to their excellent triboelectrical chargeability, 
superior friction and heating resistance, and the stability of their 
triboelectric charging function over time. 
These characteristics of triboelectrically charging members are 
specifically required in the field of electrophotographic developing 
apparatus. In dry developing apparatus which are monocomponent developers 
in particular, each time toner passes between the triboelectrically 
charging member and the developing roller, the toner must be uniformly 
thinned and adequately charged. 
Conventional triboelectrically charging members (i.e., a toner thickness 
regulating member) are subject to various disadvantages such as when toner 
fused by frictional heating adheres to the surface of the charging member 
as a mass or film. Further disadvantages include markedly reduced copy 
image quality when so-called white streaks, black streaks, filming, grainy 
fog and the like, appear in the copy image, said defects being induced by 
uneven toner thickness, insufficient toner charging and uneven charging 
which are resulted from the defects that the triboelectrically charging 
member becomes worn or its surface is damaged over time due to 
toner-induced friction. Manufactured triboelectrically charging members in 
monocomponent dry developing systems have a further disadvantage in that 
they are constructed by affixing a film or sheet made from selected 
materials to an elastic metal substrate and therefore film component 
deformation and film separation at the ends of said member readily occur 
which gives rise to the aforesaid defects causing reductions in copy image 
quality. 
Unexamined Japanese Patent Publications Sho 58-132769 and Sho 61-176961, 
for example, disclose the selections of poly-4-ethylene flouride resin or 
ethylene and 4-ethylene flouride copolymers as means for improving the 
release properties of the triboelectrically charging members. However, the 
triboelectrically charging members disclosed in these publications do not 
simultaneously fulfill requirements for release properties and friction 
resistance. 
SUMMARY OF THE INVENTION 
A main object of the present invention is to provide a triboelectrically 
charging member which has a high degree of hardness, is excellent in 
friction resistance and which can retain copy image quality over time. 
Another object of the invention is to provide a triboelectrically charging 
member which has superior release properties and can prevent adhesion of 
fused toner. 
A further object of the invention is to provide a triboelectrically 
charging member which has superior chargeability and durability with 
regard to deformation and separation. 
A still further object of the invention is to provide a triboelectrically 
charging member which can supply a toner layer of uniform thickness to the 
developing roller, and which can produce high resolution copy images with 
minimal fogging over time. 
These and other objects of the present invention are achieved by providing 
a triboelectrically charging member covered by plasma-polymerized 
amorphous carbon film containing at least carbon, hydrogen and fluorine 
atoms.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The triboelectrically charging member of the present invention functions 
effectively as a toner mixing member, developing roller, photosensitive 
member cleaning blade, and image transfer roller, but is not limited to 
the above uses. The member of the invention is especially well suited for 
use as a triboelectrically charging member in electrophotographic 
developing apparatus which employ monocomponent developers. 
The construction of a conventional monocomponent developing apparatus is 
briefly shown in FIG. 1. 
Toner 5 within the toner tank 6 is delivered via the mixing member 4 to the 
toner layer thickness regulating region formed by the developing roller 1 
and the plate-like toner thickness regulating member 3. The toner 
thickness regulating member 3 is rotatably supported by support fixture 2. 
The triboelectrically charging member 8 is provided upon the toner 
thickness regulating member 3, and makes pressure contact with the 
developing roller 1 via the action of spring 7. Developing roller 1 and 
triboelectrically charging member 8 have a fixed quantity of toner passing 
therebetween so as to produce friction, whereby a thin layer of charged 
toner having a specified thickness is formed upon the surface of said 
developing roller 1. The charged toner is delivered by developing roller 1 
to a region opposite an electrically conductive member or a photosensitive 
member which maintains an electrically latent image thereon, the toner 
then being selectively transferred to said member so as to develop the 
electrically latent image. 
In the present invention, the surface of the aforesaid triboelectrically 
charging member is covered by a plasma-polymerized amorphous carbon film 
containing at least carbon, hydrogen and fluorine atoms. 
The covering film may be obtained by plasma polymerization of a single 
compound containing at least fluorine atoms, hydrogen atoms and carbon 
atoms (hereinafter referred to as "fluorine-incorporating organic 
compound"). The covering film may also be formed by plasma polymerization 
of a mixture containing a fluorine compound such as a 
fluorine-incorporating compound (a fluorine compound may be, generally 
speaking, a compound containing fluorine but not hydrogen such as 
tetrafluoroethylene, in lieu of the aforesaid fluorine-incorporating 
organic compound) and a compound containing at least carbon and hydrogen 
atoms (compounds containing alcohol or like atoms may be used, generally 
speaking, in lieu of hydrocarbons) so as to form a plasma-polymerized film 
on the surface of the triboelectrically charging member. Plasma 
polymerization may be accomplished by vaporizing the aforesaid compounds 
and effecting a glow-discharge decomposition reaction in a vacuum, but is 
not specifically limited to this method, and may be accomplished by other 
suitable plasma polymerization means. 
Concrete examples of useful compounds capable of supplying fluorine other 
than the aforesaid fluorine-incorporating organic compounds are, for 
example, oligomers such as tetrafluoroethylene, tetrafluoromethane, 
hexafluoroethane, hexafluorocyclobutane, hexafluoropuropene, 
octafluorobutene, hexafluorocyclobutene and perfluoroalkene, and useful 
organic compounds containing halogens in addition to fluorine are, for 
example, monobromotrifluoromethane, trichlorotrifluoroethane, 
monochlorotrifluoroethylene and the like. Compounds containing oxygen and 
sulfur atoms and the like may also be used. 
Fluorine-incorporating organic compounds are compounds containing at least 
fluorine, carbon and hydrogen atoms, and may include partially fluorinated 
hydrocarbons, for example, monofluoromethane, difluoroethane, 
trifluoroethane, monofluoroethylene, monofluorobenzene and the like. Other 
halogens containing oxygen or sulfur may also be used; useful compounds 
are methacrylates and acrylates which contain fluorine atoms such as, for 
example, 2,2,2-trifluoroethylmethacrylate [CH.sub.2 
.dbd.C(CH.sub.3)COOCH.sub.2 CF.sub.3 ], 
2,2,3,3,-tetrafluoropropylmethacrylate [CH.sub.2 
.dbd.C(CH.sub.3)COOCH.sub.2 (CF.sub.2).sub.2 H], 
1H,1H,5H-octafluoropentylmethacrylate [CH.sub.2 
.dbd.C(CH.sub.3)COOCH.sub.2 (CF.sub.2).sub.4 H], 
1H,1H,2H,2H-heptadecafluorodecylmethacrylate [CH.sub.2 
.dbd.C(CH.sub.3)COO(CH.sub.2).sub.2 (CF.sub.2)F.sub.6 ], 
2,2,2-trifluoroethylacrylate [CH.sub.2 .dbd.CHCOOCH.sub.2 CF.sub.3 ], 
2,2,3,3-tetrafluoropropylacrylate [CH.sub.2 .dbd.CHCOOCH.sub.2 
(CF.sub.2).sub.2 H], 1H,1H,5H-octafluoropentylacrylate [CH.sub.2 
.dbd.CHCOOCH.sub.2 (CF.sub.2).sub.4 H, 
1H,1H,2H,2H-heptadecafluorodecylacrylate [CH.sub.2 
.dbd.CHCOO(CH.sub.2).sub.2 (CF.sub.2).sub.8 F] and the like. Flourine 
compounds containing hydrogen, i.e. fluorine-incorporating organic 
compounds, may be used singly, or when fluorine compounds do not contain 
hydrogen that may be used together with other compounds containing 
hydrogen and carbon as necessary. 
Compounds containing hydrogen and carbon are, for example, saturated 
hydrocarbons, unsaturated hydrocarbons, alicyclic hydrocarbons, aromatic 
hydrocarbons and the like, as well as alcohols, ketones, carboxyls, 
amines, amides, esters, ethers, halogenated hydrocarbons and the like. 
A wide variety of hydrocarbons are usable. Examples of useful saturated 
hydrocarbons are normal paraffins, such as methane, ethane, propane, 
butane, pentane, hexane, heptane, octane, nonane, decane, undecane, 
dodecane, tridecane, tetradecane, pentdecane, hexadecane, heptadecane, 
octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, 
tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, 
triacontane, dotriacontane, pentatriacontane, etc.; isoparaffins such as 
isobutane, isopentane, neopentane, isohexane, neohexane, 
2,3-dimethylbutane, 2-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 
2,4-dimethylpentane, 3,3-dimethylpentane, tributane, 2-methylheptane, 
3-methylheptane, 2,2-dimethylhexane, 2,2,5-dimethylhexane, 
2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 2,3,3-trimethylpentane, 
2,3,4-trimethylpentane, isononane and the like. 
Examples of useful unsaturated hydrocarbons are olefins, such as ethylene, 
propylene, isobutylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 
2-methyl-1-butene, 3-methyl-1-butene, 2- methyl-2-butene, 1-hexene, 
tetramethylethylene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like; 
diolefins such as allene, methylallene, butadiene, pentadiene, hexadiene, 
cyclopentadiene, and the like; triolefins such as ocimene, alloocimene, 
myrcene, hexatriene, and the like; and acetylene, methylacetylene, 
1-butyne, 2-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, 
1-decyne, and the like. 
Examples of useful alicyclic hydrocarbons are cycloparaffins such as 
cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 
cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, 
cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, and 
the like; cycloolifins such as cyclopropene, cyclobutene, cyclopentene, 
cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene and the 
like; terpenes such as limonene, terpinolene, phellandrene, sylvestrene, 
thujene, carene, pinene, bornylene, camphene, fenchene, cyclofenchene, 
tricyclene, bisabolene, zingiberene, curcumene, humulene, cadinene 
sesquibenihene, selinene, caryophyllene, santalene, cedrene, camphorene, 
phyllocladene, podocarpene, mirene and the like; steroids, etc. 
Examples of useful aromatic hydrocarbons are benzene, toluene, xylene, 
hemimellitene, pseudocumene, mesitylene, prehnitene, isodurene, durene, 
pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, 
cumene, styrene, biphenyl, terphenyl, diphenylmethane, triphenylmethane, 
dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, 
phenanthrene, and the like. 
The amorphous carbon film (hereinafter referred to as "a-C film") covering 
the triboelectrically charging member of the present invention is formed 
by plasma polymerization a single organic compound containing fluorine 
atoms, or plasma polymerization of a vaporized compound mixture containing 
a fluorine compound and a compound containing at least hydrogen and carbon 
so as to form an a-C film which incorporates fluorine atoms in its 
structure. A triboelectrically charging member can be prepared in this 
manner which possesses a high degree of hardness and superior surface 
release properties and which is excellent in triboelectrically 
chargeability. The triboelectrically charging member of the present 
invention is therefore damage and wear resistant, maintains copy image 
quality over time and provides a thin toner layer of uniform thickness on 
the developing roller over time, thus avoiding adhesion of fused toner on 
said developing roller. These fluorine incorporating compounds and 
hydrocarbons need not always be in a gaseous phase at room temperature and 
atmospheric pressure but can be in a liquid or solid phase insofar as they 
can be vaporized on melting, evaporation or sublimation, for example, by 
heating or in a vacuum. 
Carrier gases may be used in addition to the above compounds and 
hydrocarbons. Examples of suitable carrier gases are Ar, Ne, He and the 
like. 
According to the present invention, the gases of starting materials are 
made into an a-C film, most preferably via a plasma which is produced by 
d.c., low-or high-frequency, microwave or like plasma process. 
Alternatively, the film may be formed via ions which are produced by the 
ionization deposition, ion-beam, deposition or like process, or via 
neutral particles produced by a pressure decreasing CVD process, a vacuum 
evaporation process, sputtering process or the like. These processess may 
be used in combination. 
The triboelectrically charging member of the invention can be obtained with 
a thin uniform film since it is formed by plasma polymerization, said 
member having extremely good adhesion with the toner thickness regulating 
member. Accordingly, reliability is improved vis-a-vis separation, 
deformation and the like. 
The quantity of fluorine atoms incorporated into the a-C film of the 
invention is 1 to 70 atomic %, and preferably 2 to 40 atomic %, based on 
the total constituent atoms of the structure. When the quantity of 
fluorine atoms is less than 1 atomic %, suitable triboelectrical 
chargeability and release properties cannot necessarily be assured, and 
toner charging is reduced which gives rise to copy image fogging. When the 
quality of fluorine atoms exceeds 70 atomic %, film formability cannot be 
assured and film separation, oiliness and powdering may result. 
Further, a triboelectrically charging member having different triboelectric 
charging characteristics can be obtained by varying the quantity fluorine 
atoms contained by the a-C film. 
The quantity of fluorine atoms contained in the a-C film of the present 
invention can be controlled, in the case of plasma-polymerization of a 
vaporized fluorine-incorporating organic compound only, by using compounds 
which have different fluorine contents, or by selectably changing the 
conditions of the plasma polymerization process. When film formation is 
performed together with hydrocarbon compounds, the quantity of fluorine 
atoms incorporated in the a-C film is chiefly controlled by increasing and 
decreasing the volume of said gaseous fluorine mixture introduced into the 
reactor wherein the plasma polymerization reaction occurs. When the inflow 
volume of the aforesaid gas is increased, the quantity of fluorine atoms 
added to the a-C film to the invention can be increased, and conversely, 
when the input volume of said compound is reduced, the quantity of 
fluorine atoms added to the a-C film of the invention can be decreased. 
The hydrogen content of the a-C film of the invention is variable in 
accordance with the film forming apparatus and film forming conditions. 
The hydrogen content can be decreased, for example, by elevating the 
substrate temperature, lowering the pressure, reducing the degree of 
dilution of the starting materials, applying a greater power, decreasing 
the frequency of the altering electric field to be set up, increasing the 
intensity of a d.c. electric field superposed on the alternating electric 
field, or a desired combination of such procedures. 
More specifically, the hydrogen content is about 0.1 to 67 atomic %, more 
preferably about 1 to 60 atomic %, and most preferably about 30 to 60 
atomic %, based on all the constituent atoms in the film. If the hydrogen 
content exceeds 67 atomic %, film formation decreases, whereas a hydrogen 
content below 0.1 atomic % leads to lower chargeability. 
The structure of the a-C film of the present invention and the contents of 
carbon, hydrogen and fluorine atoms therein can be determined by a usual 
method of elementary analysis, for example, by organic elementary 
analysis, Auger electron spectroscopy, infrared absorption spectrum 
analysis, x-ray analysis, .sup.1 H-NMR, .sup.13 C-NMR and the like. 
The thin a-C film of the invention having a thickness of about 1 to 200 
.mu.m, preferably about 5 to about 100 .mu.m, can impart a satisfactory 
charge to the toner, and can also form a thin toner layer. When the a-C 
film is less than 1 .mu.m in thickness, triboelectrical chargeability is 
reduced and the toner cannot be adequately charged, whereas a thickness 
which exceeds 200 .mu.m is undesirable from a production standpoint. 
FIG. 2 shows an apparatus for producing the a-C film of the present 
invention. The first to sixth tanks 701 to 706 in the drawing have 
enclosed therein starting material compounds which are in gas phase at 
room temperature and a carrier gas, and are connected respectively to the 
first to sixth regulator valves 707 to 712 and first to sixth flow 
controllers 713 to 718. First to third containers 719 to 721 contain 
starting material compounds which are liquid or solid at room temperature, 
which can be preheated by first to third heaters 722 to 724 for vaporizing 
the compounds, and are connected to the seventh to ninth regulator valves 
725 to 727 and the seventh to ninth flow controllers 728 to 730, 
respectively. The gases to be used as selected from among these gases are 
mixed in a mixer 731 and fed to a reactor 733 via a main pipe 732. The 
interconnecting piping can be heated by a pipe heater 734 which is 
suitably disposed so that the material compound, in a liquid or solid 
phase at room temperature and vaporized by preheating, will not condense 
during transport. A grounded electrode 735 and a power electrode 736 are 
so arranged that they oppose each other within the reactor 733. Each of 
these electrodes can be heated by an electrode heater 737. The power 
application electrode 736 is connected to a high-frequency power source 
739 via a high-frequency power matching device 738, to a low-frequency 
power source 741 via a low-frequency power matching device 740, and to a 
direct current power source 743 via a low-pass filter 742. Power of one of 
the different frequencies is applicable to the electrode 736 by way of a 
connection selecting switch 744. The internal pressure of the reactor 733 
is adjustable by a pressure control valve 745. The reactor 733 is 
evacuated by a diffusion pump 747 and an oil rotary pump 748 via an 
exhaust system selecting valve 746, or by a cooling-removing device 749, a 
mechanical booster pump 750 and an oil rotary pump 748 via the exhaust 
system selecting valve 746. The exhaust gas is further made harmless by a 
suitable removal device 753 and then released to the atmosphere. The 
evacuation piping system can also be heated by a suitably disposed pipe 
heater 734 so that the material compound which is liquid or solid at room 
temperature and vaporized by preheating will not condense during 
transport. For the same reason, the reactor 733 can also be heated by a 
reactor heater 751. An electrically conductive substrate 752 is placed on 
the electrode in the reactor. Although FIG. 2 shows that the substrate 752 
is fixed to the grounded electrode 735, the substrate may be attached to 
the power application electrode 736 or to both electrodes. 
The reactor for preparing the a-C film is first evacuated by the diffusion 
pump to a vacuum of about 10.sup.-4 to about 10.sup.-6 torr, whereby the 
absorbed gas within the reactor is removed. The reactor is also checked 
for the degree of vacuum. At the same time, the electrodes and the 
substrate fixedly placed on the electrode are heated to a predetermined 
temperature by the electrode heater. Subsequently, material gases are fed 
into the reactor from the first to sixth tanks and first to third 
containers (i.e. from those concerned) each at a specified flow rate using 
the first to ninth flow controllers, and the interior of the reactor is 
maintained in a predetermined vacuum by the pressure control valve. After 
the combined flow of gases has become stabilized, the high-frequency power 
source, for example, is selected by the connection selecting switch to 
apply a high-frequency power to the power application electrode. This 
initiates a discharge across the two electrodes, forming a solid film on 
the substrate with time. The thickness of the film is controllable by 
varying the reaction time, such that the discharge is discontinued upon 
the thickness reaching the desired value. 
Next the regulator valves concerned are closed, and the reactor is 
throughly exhausted. When an a-C film of the desired structure has been 
formed according to the invention, the vacuum within the reactor is 
vitiated and the film is removed from the reactor. 
The a-C film of the present invention may contain alkaline metals or 
elements in Groups IIIA or VA of the Periodic Table of the Elements as a 
chemical modifier. Doping of such dopants improves triboelectrical 
chargeability. 
The present invention will be described hereinafter with reference to the 
following examples. 
Example 1 
Film Forming Step 
The glow discharge decomposition apparatus shown in FIG. 2 was used. First 
the interior of the reactor 733 was evacuated to a high vacuum of 
approximately 10.sup.-6 torr, and the seventh regulator valve 725 was 
thereafter opened to introduce 1H,1H,5H-octafluoropentylmethacrylate 
[CH.sub.2 .dbd.C(CH.sub.3)COOCH.sub.2 (CF.sub.2).sub.4 H] gas, heated by 
the first heater 722 to a temperature of 75.degree. C., from the first 
container 719 into the seventh flow controller 728. The dial on the flow 
controller was adjusted to supply the 
1H,1H,5H-octafluoropentylmethacrylate gas at a flow rate of 6.8 sccm to 
the reactor 733 through the main pipe 732. Following stabilization of the 
gas flow, the internal pressure of the reactor 733 was adjusted to 0.25 
torr by the pressure control valve 745. On the other hand, the substrate 
752 was used, said substrate being a ribbon-shaped steel material 
measuring 30 mm in length, 230 mm in width and 0.2 mm in thickness, was 
preheated to 160.degree. C. With the gas flow rate and the pressure in 
stabilized states, 100-watt power with a frequency of 30 KHz was applied 
to the power application electrode 736 from the low-frequency power source 
741 pre-connected thereto by the selecting switch 744 to conduct plasma 
polymerization for approximately 180 min, forming an a-C film 9 .mu.m in 
thickness on the substrate 752, whereupon the power supply was 
discontinued, the regulator valves were closed, and the reactor 733 was 
fully exhausted. 
When subjected to quantitative analysis, the a-C film thus obtained was 
found to contain 31 atomic % of hydrogen atoms, 24 atomic % of fluorine 
atoms and 5 atomic % of oxygen atoms based on the total combined 
constituent atoms therein. 
Further, this film has an infrared absorption spectrum shown in FIG. 3. 
Moreover, upon measurement of the hardness by a pencil durometer, this film 
was found to have a hardness rating of 6H. 
Characteristics: 
When the obtained ribbon-shaped steel substrate covered by the a-C film was 
installed as a toner thickness regulating member in a monocomponent 
developing apparatus in an electrophotographic copying machine and 
subjected to copy image formation and transfer in a normal Carlson 
process, sharp, high resolution copy images were obtained without any 
traces of striped irregularities in image density, grainy fog, or whiteout 
lines. 
Furthermore, the same sharp copy images were obtained after 100,000 copies. 
No damage, wear or toner adhesion was observed under microscopic 
examination. 
It is understood from the above results that the plasma-polymerized film of 
the present invention as described in the present example possesses 
excellent performance as a triboelectrically charging member. 
Examples 2 to 10 
The a-C films were prepared in substantially the same manner as described 
in Example 1. 
Table 1 shows the various condition values for forming an a-C film. 
More specifically, Table 1 shows the conditions which are different from 
Example 1 for forming an a-C film, said differences being classified into 
17 items labeled 1 to 17. These items are described at the top column of 
Table 1. Some of the condition values shown in each item are common to 
each example, while others vary in each example. 
Table 1 shows the items 1 to 17 as follows: 
(1) Flow rate of hydrogen gas from the first tank 701 (sccm) 
(2) Flow rate of material gas from the second tank 702 (sccm) 
(3) Flow rate of dopant gas from the third tank 703 (sccm) 
(4) Flow rate of dopant gas from the first container 719 (sccm) 
(5) Flow rate of dopant gas from the second container 720 (sccm) 
(6) Temperature of the first heater 722 (.degree. C.) 
(7) Temperature of the second heater 723 (.degree. C.) 
(8) Pressure (torr) 
(9) Temperature of the substrate (.degree. C.) 
(10) Dimension of the substrate (length.times.width .times.thickness) 
(unit: mm) 
(11) Frequency from the power source (Hz) 
(12) Time for plasma polymerization 
(13) Power (watt) 
(14) Thickness of the film (micron) 
(15`) Hardness (H) 
(16) Hydrogen content (atomic %) P1 (17) & (18) Content of the dopant 
contained in the a-C film (atomic %) 
When the characteristics of the triboelectrically charging members obtained 
in Examples 2 to 10 were examined in the same manner as described in 
Example 1, results similar to those of Example 1 were obtained. 
It is understood from the above examples that plasmapolymerized film of the 
present invention possesses excellent properties as a triboelectrically 
charging member. 
TABLE 1 
__________________________________________________________________________ 
Ex. 
(1) 
(2) (3) 
(4) (5) (6) 
(7) 
(8) 
(9) 
(10) 
No. 
sccm 
sccm 
sccm 
sccm 
sccm 
.degree.C. 
.degree.C. 
Torr 
.degree.C. 
mm 
__________________________________________________________________________ 
2 -- -- -- (A)10 
-- 75 -- 0.25 
160 
30 .times. 230 .times. 
0.2 
3 -- -- -- (A)15 
-- 75 -- 0.25 
160 
30 .times. 230 .times. 
0.2 
4 -- -- -- (A)6.8 
-- 75 -- 0.25 
250 
30 .times. 230 .times. 
0.2 
5 -- -- -- (A)6.8 
-- 75 -- 0.25 
250 
30 .times. 230 .times. 
0.2 
6 -- -- -- (B)20 
-- 30 -- 0.25 
250 
30 .times. 230 .times. 
0.2 
7 H.sub.2 40 
C.sub.2 H.sub.4 30 
CF.sub.4 
-- -- -- -- 1.0 
250 
30 .times. 230 .times. 
120 0.2 
8 H.sub.2 40 
C.sub.2 H.sub.4 30 
-- (A)10 
-- 70 -- 0.8 
200 
30 .times. 230 .times. 
0.2 
9 -- -- -- (A)20 
C.sub.5 H.sub.8 70 
70 40 0.9 
100 
30 .times. 230 .times. 
0.2 
10 H.sub.2 60 
C.sub.4 H.sub.6 20 
-- (A)20 
-- 70 -- 1.0 
200 
30 .times. 230 .times. 
0.2 
__________________________________________________________________________ 
Ex. (11) (13) 
(14) 
(15) 
(16) (17) (18) 
No. Hz (12) watt 
.mu.m 
H at. % 
at. % at. % 
__________________________________________________________________________ 
2 30K 180 m 
100 
12 6 17 F 29.5 
0 3.3 
3 30K 180 m 
100 
20 7 10 F 38 0 1.2 
4 30K 180 m 
100 
4 7 22.5 F 13.6 
0 0.8 
5 13.56 M 
60 m 
50 
10.5 
5 33.5 F 23 0 4.5 
6 13.56 M 
60 m 
50 
20 6 34 F 17.5 
0 5.5 
7 13.56 M 
5 h 200 
20 7 47 F 3.1 -- 
-- 
8 50 K 3 h 100 
13 6 48 F 12.6 
-- 
-- 
9 30 K 30 m 
50 
25 6 44 F 5.7 -- 
-- 
10 200K 45 m 
100 
25 6 35 F 15 -- 
-- 
__________________________________________________________________________ 
(1) (A) means 1H, 1H, 5H octafluoropenthylmethacrylate [CH.sub.2 
.dbd.C(CH.sub.3)COOCH.sub.2 (CF.sub.2).sub.4 H] gas. 
(2) (B) means 2, 2, 2 trifluoroethylmethacrylate [CH.sub.2 
.dbd.C(CH.sub.3)COOCH.sub.2 CF.sub.3 ] gas. 
(3) C.sub.2 H.sub.4 at column (2) means ethylene. 
(4) C.sub.4 H.sub.6 at column (2) means butadiene. 
(5) C.sub.5 H.sub.8 at column (5) means stylene. 
Comparative Example 
Ribbon-shaped steel substrates (30.times.230.times.0.2 mm) had the 
following films approximately 100 .mu.m in thickness affixed to their 
surfaces by adhesive tape: 
(A) polytetrafluoroethylene film 
(B) silicon resin film 
(C) polyamide resin film 
When the above members were tested by the methods described in Example 1, 
copy image quality deteriorated after several thousand copies with the 
appearance of striped irregularities in image density, whiteout lines, 
grainy fog and black lines in the image background. 
Further, macroscopic and microscopic examinations revealed line-shaped 
wearing of the film, and mass or film-like toner adhesion to said layer.